Curable material comprising silylated polymers containing urethane groups, and use thereof in sealants, adhesives, binders and/or surface modifiers

ABSTRACT

Curable material comprising silylated polymers containing urethane groups, and use thereof in sealants, adhesives, binders and/or surface modifiers.

This application claims benefit under 35 U.S.C. 119(a) of German patentapplication DE 10 2009 028640.3, filed on Aug. 19, 2009.

Any foregoing applications including German patent application DE 102009 028640.3, and all documents cited therein or during theirprosecution (“application cited documents”) and all documents cited orreferenced in the application cited documents, and all documents citedor referenced herein (“herein cited documents”), and all documents citedor referenced in herein cited documents, together with anymanufacturer's instructions, descriptions, product specifications, andproduct sheets for any products mentioned herein or in any documentincorporated by reference herein, are hereby incorporated herein byreference, and may be employed in the practice of the invention.

The invention relates to the use of innovative curable materialscomprising reaction products containing urethane groups and obtainablefrom silyl polyethers and compounds bearing isocyanate groups, forsurface modification and surface coating, for the production ofsealants, adhesives and binders, and for polyurethane systems, and alsoto processes for preparation thereof.

To a person skilled in the art, there are numerous known types ofcurable materials or reactive prepolymers, tailored to the particulararea of application. In all cases, compounds are involved that containreactive, curable and/or crosslinkable functional groups, such asepoxide, amino, hydroxyl, isocyanate, acrylate, vinyl, allyl or silylgroups, for example. Among these very different types of prepolymers,the moisture-curing systems which bear silyl groups and/or isocyanategroups possess a prominent economic importance.

Among the most important applications of reactive curable materials istheir use as adhesives, as sealants, as binders or as modifiers forsurfaces.

Modification for the purposes of this invention includes surfacecoatings as well, which in general are full-area coatings, as in thecase of paints and inks, for example, and/or in water repellants.

Similarly diverse are the substrates amenable to surface modification.As well as fairly flat carrier materials such as metals, concrete,plastics, wood or glass, there are solid particles, fibres and, forexample, textile fabrics that are surface modified by application ofthin layers.

Thus it is prior art to modify surfaces of inorganic particles,macroscopic inorganic surfaces and inorganic fibres, such as those ofmetal oxides, mixed oxides, nitrides, hydroxides, carbides, carbonates,silicates, pigments, carbon blacks, elements or alloys, for example.Likewise known to a person skilled in the art is the modification oforganic particles, natural materials in small-particle form, macroscopicorganic surfaces and fibres, such as those of silicone resins,organically modified silicones, organic polymers or biopolymers, forexample.

It can be particularly advantageous if the curable material contains atleast one functional group which is able to enter into covalent, ionicor coordinative bonds or hydrogen bonds with the surface that is to bemodified. These functional groups may be, for example, carboxylic acidgroups, OH groups, SH groups, epoxide groups, amino groups, SiOH groups,isocyanate groups or hydrolysable alkoxysilanes.

It is of particular advantage if at the same time, on the surface of thesubstrate, there are functional groups present such as hydroxyl groups,SH groups, amino groups or, for example, carboxylic acid groups, withthe result that there may be intensive physical interactions developedor else there are chemical reactions between reactive functional groupsof the curable material with those on the substrate surface. In this waythe curable material is anchored permanently to the substrate inquestion.

The type of anchor group in the curable material must be tailored ineach case precisely to the nature and the type of the reactivefunctional groups of the substrate surface. Important further selectioncriteria for the choice of most suitable curable material are the pH,moisture content or porosity of the substrate in question.

Consequently, rather than one chemical system which can be useduniversally for all types of surfaces, there are a multiplicity ofclasses of compound which bear reactive groups and which are employedfor surface modification. The prior art lists, for example, reactivemonomeric and polymeric isocyanate-, epoxide-, acrylate-, silane-,carboxylate-, amine-, hydroxyl- and mercapto-functional compounds, whichare each fixed on the substrate in different chemical/physical waysdepending on the substrate.

An important part as sealants, adhesives, binders and/or coatingconstituents is played by reactive curable materials, more particularlythose which contain moisture-crosslinking isocyanate functions and/oralkoxysilane functions.

Polymers and oligomers prepared from compounds bearing isocyanate groupsby reaction with hydroxyl- or amino-functional compounds are known ingreat chemical diversity. Depending on the stochiometry of the reactionand the nature of the starting compounds, this produces prepolymerswhich contain urethane and/or urea groups and, terminally, bear reactiveisocyanate, hydroxyl or amine groups, and which in synthesis can eitherbe reacted further in a subsequent step or else frequently can be usedas crosslinkable base materials for adhesives and sealants or else ascoating materials.

Particularly widespread and of economic importance areisocyanate-terminated urethane prepolymers which are formed through thereaction of a polyether polyol with molar excesses of an organicdiisocyanate monomer, and in which, if desired, the excess diisocyanatemonomer is removed by distillation. Based on such prepolymers, forexample, are the specifications GB 1,101,410 and U.S. Pat. No.5,703,193, U.S. Pat. No. 4,061,662, U.S. Pat. No. 4,182,825, U.S. Pat.No. 4,385,171, U.S. Pat. No. 4,888,442 and U.S. Pat. No. 4,288,577.

The introduction of urethane groups into the prepolymer structure allowsthe known high resistance of the polyurethanes to solvents, chemicalsand effects of weathering, and their high mechanical flexibility, to betransposed to the isocyanate-based sealants and adhesives. Besides thepolyurethane prepolymers which bear NCO groups, there are alsosilane-terminated polyurethanes known which according to the prior artno longer contain any free NCO groups. Reacting an isocyanate prepolymerwith alkoxysilanes bearing, for example, amino groups produces ureagroups as a link between the prepolymer and the actual desired curableterminal alkoxysilyl groups.

Alkoxysilane-functional polyurethanes may be prepared in accordance withU.S. Pat. No. 3,627,722 or U.S. Pat. No. 3,632,557, by reaction, forexample, of polyether polyols with an excess of polyisocyanate to givean NCO-containing prepolymer, which is then further reacted in turn withan amino-functional alkoxysilane.

DE 10 2005 041954 A1 (US 2007-0055010) describes urethane prepolymerswhich contain alkoxysilyl groups, which are allophanate-modified, andwhose allophanate structure contains a moisture-curing silane-functionalradical.

The teaching of DE 10 2006 054 155 (US 2010-0078117) provides for theaddition of free silanes as additional components to the trialkoxysilylunits already represented in the copolymer structure; these free silanestake on the function of water scavenges (improving shelf life),crosslinkers, reactive diluents or, for example, adhesion promoters.

Dow Chemical, in U.S. Pat. No. 6,162,862, describes polyfunctional,liquid, urethane-containing adducts which in addition to an isocyanatefunction may also include a silyl function, as surface coating materialsand paint constituents.

Disadvantageous in the sense of good substrate adhesion of the adhesivebond, of the sealant or, for example, of the surface coating material isthe low density of functionalization of the prior-art prepolymersterminated with silyl groups only in α,ω-position. The known isocyanateprepolymers as well have crosslinkable NCO groups at their chain endsonly.

The use of alkoxysilane-functional prepolymers for preparingsilane-crosslinking rigid foams and flexible foams, especiallyisocyanate-free, sprayable assembly foams, is known and is described inEP 1 098 920 B1 or EP 1 363 960 B1 (U.S. Pat. No. 7,674,840), forexample. These spray foams are typically applied from pressurized cansand serve generally to fill and seal cavities in a construction.

DE 10 2006 054 155 (US 2010-0078117) teaches a method of adhesivelybonding surfaces that uses foamable mixture of silane-terminatedprepolymers and blowing agent.

Alkoxysilane-terminated, moisture-curing, one-component polyurethanesare increasingly being used as flexible coating, sealing and bondingcompositions in construction and in the automotive industry.

Surface modifiers or curable materials, sealants and adhesivescomprising compounds which bear silane groups can be applied in pureform, in solution in an organic solvent, in formulations or else as anaqueous emulsion. Emulsions of silylated prepolymers are subject matterof a multiplicity of specifications. Specification DE 2558653 describesemulsions comprising self-emulsifying polyurethanes bearing silylgroups, and their use for the coating of surfaces. Specification JP1318066 describes aqueous emulsions of silylated polyethers which mayfurther comprise colloidal silica. DE 4215648 discloses storage-stablecontact adhesives based on solutions or emulsions of cationicallymodified, alkoxysilane-terminated polyurethanes.

In widespread use are low-viscosity monomeric alkoxysilane compounds ofthe formula (1),U_(x)SiV_((4-x))  (1)where U represents identical or different groups which arenon-hydrolysable in the presence of water and optionally catalyst, and Vrepresents identical or different groups which are hydrolysable in thepresence of water and optionally catalyst, or hydroxyl groups, and xrepresents 1, 2, 3 or 4. Such compounds include, for example, thosebearing the trimethoxysilyl and triethoxysilyl groups.

So-called α-silane-terminated polymers, whose reactive alkoxysilyl groupis separated only by one methylene unit from a urethane group, aredescribed by WO 2005/100482 and EP-A1-1 967 550 (US 2009-0088523).

Also known are silane polymers in which the silane groups are separatedterminally by a propylene unit from a urethane group to which a polymerbackbone is attached. Preference in this context is given topolyalkylene oxides, especially polypropylene glycols having silanefunctions on each of the two chain ends, as described in EP-A1-1 824 904(US 2009-0264612).

Likewise known are silane-terminated polyurethanes, whose preparationfrom a polyol by reaction with a diisocyanate and, subsequently, with anamino-functional alkoxysilane is described in U.S. Pat. No. 7,365,145,U.S. Pat. No. 3,627,722 or U.S. Pat. No. 3,632,557, for example. Thelinking group in this case is a radical which bears urethane groups andurea groups.

The skilled person also knows of urethane-free and urea-free,silyl-terminated polyethers, in which the terminal alkoxysilyl groupsare attached via an ether function directly to the polymer backbone, asdescribed in U.S. Pat. No. 3,971,751. They are composed preferably of apolyether backbone and are available as MS Polymer® products fromKaneka. Polysiloxanes bearing alkoxysilyl groups, too, as described inWO 2007/061847 (US 2008-0306208), for example.

Known, furthermore, are hydroxyl compounds which bear alkoxysilyl groupsand are prepared by alkoxylating epoxy-functional alkoxysilanes overdouble metal cyanide (DMC) catalysts in accordance with the as yetunpublished specification DE 10 2008 000360.3 (U.S. Ser. No.12/389,667). Their use as optionally foamable adhesives and sealants,and also coating materials, is described in the as yet unpublishedspecification DE 10 2008 043218.0 (U.S. Ser. No. 12/561,599). The as yetunpublished specification DE 10 2009 022628.1 (U.S. Ser. No. 12/630,125)discloses methods of modifying sheet and particle surfaces by means ofhydroxyl compounds bearing silyl groups. The as yet unpublishedspecification DE 10 2009 022627.3 (PCT/EP2010/055508) describes the useof the polyethers obtained from epoxy-functional alkoxysilanes asceramic binders, especially for producing refractory materials. Alsoknown is the preparation, as disclosed in the as yet unpublishedspecification DE 10 2009 022630.3 (PCT/EP2010/055495), of aqueousemulsions and their applications as raw materials, for example, forpaints, adhesives, cosmetic products, coatings, architecturalpreservatives, and sealants. As set out in the as yet unpublishedspecification DE 10 2009 022631.1 (PCT/EP2010/055502), curablecompositions of the silyl polyethers prepared in accordance with DE 102008 000360.3 (U.S. Ser. No. 12/389,667) are also known, as is theirapplication as base materials for the preparation of adhesives andsealants, for surface coating and surface modification, as reactivecrosslinkers, as adhesion promoters, spreaders and, for example,primers.

In view of the high molecular mass construction, the silyl modificationof the polymers is not sufficient to ensure the desired good substrateadhesion. Accordingly, the teaching of DE 10 2006 054 155 (US2010-0078117) refers to the option of adding free silanes to the PUmatrix in order to bring forth the desired effects discussed at theoutset (promotion of adhesion, drying, crosslinking, and the like). Thisby no means ensures the targeted installation of silane anchor groups atthose locations in the polymer that require their positive effect.

There is therefore demand for a technically simple, reliable and, inparticular, reproducible process. The known processes are lacking infreedom to provide access, away from the known α,ω-functionalizationprinciple, to prepolymer structures which possess a molecular presenceof curable moieties (i.e. sum of isocyanato functions and silylfunctions per molecule) of more than 2 and, furthermore, an opportunityfor choice, at the desire of the synthetic chemist, to tailor the ratioof the curable moieties (isocyanato/alkoxysilyl functions) to oneanother to the target performance requirements, within wide ranges.

Moreover, it is a deficiency known to the skilled person thatconventional silyl-terminated polyurethanes, owing to the high viscositywhich they have as a result of their chemical construction, arerestricted in their possible applications, as emphasized in U.S. Pat.No. 7,365,145. This is so in particular when, in the field of sealantand adhesive systems, conventional amounts of 30-50% by weight ofinorganic fillers such as calcium carbonate or silicates are added. Inaccordance with the prior art, therefore, diluents are added to polymersof this type. These may be either reactive diluents, which not onlylower the viscosity but also raise the crosslinking density at the sametime, such as monomeric alkoxy silanes, or may be non-reactive diluentsor solvents, which may additionally have plasticizing properties. Onetypical representative of this class of silyl-terminated polyurethanesis, for example, Desmoseal® S XP 2636 from Bayer Material Science,having a viscosity of around 40 000 mPas (23° C.).

Using targeted allophanatization, the prior art attempts to counteractthe high viscosities, which are a result of strong intermolecularhydrogen bonds and dipolar interactions between the urethane and, wherepresent, urea units, but without being able to eliminate the deficitrepresented by the low crosslinking density.

WO 2007/025667 (US 2007-0055010) describes modified polyurethaneprepolymers which contain alkoxysilane groups and are said to have asignificantly reduced viscosity. A disadvantage, however, is therelatively low density of crosslinkable silyl groups.

With acknowledgement of the state of the art as set out herein, thetechnical problem to be solved is defined as that of providinginnovative sealants and adhesives, binders and modifiers, comprisingsilylated prepolymers containing urethane groups, which, throughcomparatively lower viscosities, avoid the disadvantages ofalkoxysilane-modified polyurethane prepolymers described.

The problem is solved by means of innovative curable materialscomprising reaction products of alkoxysilyl compounds and isocyanates.

The present invention accordingly provides innovative curable materialscomprising urethane-group-containing (pre)polymers and/or reactionproducts, obtainable through the reaction of

-   a) at least one compound containing one or more isocyanate groups    with-   b) at least one compound bearing one or more alkoxysilyl groups and    additionally bearing at least one hydroxyl group,-   c) optionally in the presence of one or more catalysts,-   d) optionally in the presence of further components reactive towards    the reaction products, more particularly those components which    possess functional groups having protic hydrogen, such as, for    example, alcohols, amines, thiols, organofluorine hydroxy compounds,    alkoxysilanes and/or water,-   e) optionally in the presence of further compounds which are not    reactive towards the reaction products and reactants, such as, for    example, solvents, process assistants and/or suspension agents, and    also preparations comprising these curable materials.

The present invention accordingly provides curable materials comprisingurethane-group-containing polymer preparations, obtainable through thereaction of one or more compounds containing isocyanate groups with oneor more compounds bearing alkoxysilyl groups and hydroxyl groups.

In one preferred embodiment the component (a) containing isocyanategroups bears no alkoxysilyl and/or alkylsilyl groups.

Preferred curable materials comprise alkoxysilyl-modified,urethane-group-containing reaction products which are characterized inthat, based on the individual molecule of the reaction product, there ison average more than 1 alkoxysilyl group per urethane group or reactionderivatives thereof, such as, for example allophanates and/or biuretgroups or else urea groups. As component b) it is preferred to use silylpolyethers of the formula 1 having an index d of greater than or equalto 1.

The invention further provides for the use of theurethane-group-containing curable materials as a constituent of curablesealants and adhesives, binders and modifiers, and the thus-preparedsealants and adhesives, binders and modifiers themselves, it beingpossible for the alkoxysilyl groups to be present, optionally, singly ormultiply, and terminally or within the polymer chain, and it also beingpossible, optionally, for additional isocyanate groups to be presentterminally.

By virtue of their application properties such as reactivity,crosslinking density, adhesion, mechanical properties and, for example,viscosity, the resultant innovative sealants and adhesives, binders andmodifiers allow flexible attachment via the polymer structure to theparticular substrate to be modified or to the surfaces to be bonded orto be sealed.

A particular feature of these innovative sealants and adhesives, bindersand modifiers is that they can optionally be modified further not onlyvia the isocyanate groups and/or hydroxyl groups they contain but alsovia the alkoxysilyl groups that are incorporated in them.

A further aspect of this invention involves providing a technicallysimple and economic process for preparing these new sealants andadhesives, binders and modifiers. This invention providesurethane-group-containing, innovative sealants and adhesives, bindersand modifiers which are obtained through the reaction of one or morecompounds containing isocyanate groups with one or more compoundsbearing alkoxysilyl and hydroxyl groups, especially silyl polyethers 1(formula 2).

A silyl group for the purposes of this invention is characterized inthat as well as at least one alkoxy function it has one or two alkylfunctions or one or two further alkoxy functions on a silicon atom, andthe organic or oxyorganic groups present in these radicals may be alikeor different.

The preparation of the silyl polyethers 1, and the types of epoxidestructure that can be used, are described comprehensively in DE 10 2008000360.3, unpublished at the priority date of the present specification,and, accordingly, can be prepared by alkoxylating epoxy-functionalalkoxysilanes over double metal cyanide catalysts, for example.Reference is hereby made to the content of the description and claims ofDE 10 2008 000360.3 in their entirety, and the aforementionedspecification is considered to be part of the present disclosure.

The invention therefore further provides a curable material, comprisingas component (b) one or more silyl polyethers 1 of the formula 2:

where

-   a is an integer from 1 to 3, preferably 3,-   b is an integer from 0 to 2, preferably 0 to 1, more preferably 0,    and the sum of a and b is 3,-   c is an integer from 0 to 22, preferably from 0 to 12, more    preferably from 0 to 8, very preferably from 0 to 4, and more    particularly 1 or 3,-   d is an integer from 1 to 500, preferably 1 to 100, more preferably    2 to 20, and with particular preference 2 to 10,-   e is an integer from 0 to 10 000, preferably 1 to 2000, more    preferably 2 to 2000, and more particularly 2 to 500,-   f is an integer from 0 to 1000, preferably 0 to 100, more preferably    0 to 50, and more particularly 0 to 30,-   g is an integer from 0 to 1000, preferably 0 to 200, more preferably    0 to 100, and more particularly 0 to 70,-   h, i and j independently of one another are integers from 0 to 500,    preferably 0 to 300, more preferably 0 to 200, and more particularly    0 to 100,-   n is an integer between 2 and 8, and with the proviso that the    fragments having the indices d to j are freely permutable with one    another, i.e. exchangeable for one another in the sequence within    the polyether chain, and-   R is one or more identical or different radicals selected from    linear or branched, saturated, singly or multiply unsaturated alkyl    radicals having 1 to 20, more particularly 1 to 6 carbon atoms or    haloalkyl groups having 1 to 20 carbon atoms. Preferably R    corresponds to methyl, ethyl, propyl, isopropyl, n-butyl and    sec-butyl groups; and also-   R¹ is a hydroxyl group or a saturated or unsaturated linear,    branched or cyclic or further-substituted oxyorganic radical having    1 to 1500 carbon atoms, it also being possible for the chain to be    interrupted by heteroatoms such as O, S, Si and/or N, or a radical    comprising an oxyaromatic system, preferably an alkoxy, arylalkoxy    or alkylarylalkoxy group and more particularly a polyether radical,    in which the carbon chain may be interrupted by oxygen atoms, or a    singly or multiply fused oxyaromatic group or an optionally    branched, silicone-containing organic radical,-   R² or R³, and also R⁵ or R⁶, are, identically or else independently    of one another, H and/or a saturated or optionally singly or    multiply unsaturated, including further-substituted, optionally    monovalent or polyvalent hydrocarbon radical, the radicals R⁵ or R⁶    being a monovalent hydrocarbon radical. The hydrocarbon radical may    be bridged cycloaliphatically via the fragment Y; Y may be absent,    or else may be a methylene bridge having one or two methylene units;    if Y is absent, then R² or R³ independently of one another are a    linear or branched radical having 1 to 20, preferably 1 to 10 carbon    atoms, more preferably a methyl, ethyl, propyl or butyl, vinyl,    allyl radical or phenyl radical. Preferably at least one of the two    radicals, R² or R³, is hydrogen. R²-R³ may be a —CH₂CH₂CH₂CH₂ group,    and Y therefore a —(CH₂CH₂—) group. The hydrocarbon radicals R² and    R³ may in turn be further substituted and may carry functional    groups such as halogens, hydroxyl groups or glycidyloxypropyl    groups.-   R⁴ independently at each occurrence is a linear or branched alkyl    radical of 1 to 24 carbon atoms or an aromatic or cycloaliphatic    radical, which optionally may in turn carry alkyl groups;-   R⁷ and R⁸ are independently of one another either hydrogen or alkyl,    alkoxy, aryl or aralkyl groups,-   R⁹, R¹⁰, R¹¹ and R¹² are independently of one another either    hydrogen or alkyl, alkenyl, alkoxy, aryl or aralkyl groups. The    hydrocarbon radical may be bridged cycloaliphatically or    aromatically via the fragment Z, it being possible for Z to    represent a divalent alkylene radical or else alkenylene radical,    with the proviso that the fragments having the indices d, e, f    and/or h are freely permutable with one another, i.e. are    interchangeable with one another within the polyether chain and may    be present alternatively with statistical distribution or blockwise    sequencing, and hence are interchangeable with one another in the    sequence within the polymer chain.

Preferred silyl polyethers 1 are those in which the sum of the fragmentsd to j is greater than or equal to 3, if R¹ is composed only of onemonomer or oligomer.

In the absence of a nomenclature which describes their compositionspecifically, the compounds of the formula (2) are referred to below assilyl polyethers 1, even if the structure may not encompass the featuresof a polymeric ether in the conventional sense. For the skilled person,however, the structural coincidence of polyether structural elementswith those of the silyl polyethers 1 is clearly and distinctly apparent.

In the context of this invention, the term “polyethers” embraces notonly polyethers, polyetherols, polyether alcohols and polyether estersbut also polyether carbonates, which, where appropriate, are usedsynonymously with one another. In such cases it is not necessary for theexpression “poly” to necessarily imply that there are a multiplicity ofether functionalities or alcohol functionalities present in the moleculeor polymer. Instead, this expression merely indicates that there are atleast repeating units of individual monomer building blocks or elsecompositions which have a relatively high molar mass and also,furthermore, a certain polydispersity.

The word-fragment “poly” in connection with this invention encompassesnot only exclusively compounds having at least three repeating units ofone or more monomers in the molecule, but also, in particular, thosecompositions of compounds which have a molecular weight distribution andpossess an average molecular weight of at least 200 g/mol. Thisdefinition takes account of the circumstance that, within the field ofart under consideration, it is customary to designate even compounds ofthis kind as polymers, even when they do not appear to satisfy thedefinition of a polymer along the lines of OECD or REACH guidelines(e.g. European Regulation No. 1907/2006).

R¹ is a fragment which comes from the starter, or starter compounds, forthe alkoxylation reaction, as per formula (3)R¹—H  (3)(the H belongs to the OH group of an alcohol or phenolic compound);starters of the formula (3) may be used alone or in mixtures with oneanother, and have at least one reactive hydroxyl group; hence thestarter may also be water.

OH-functional starter compounds R¹—H (3) used are preferably compoundshaving molar masses of 18 (water) to 10 000 g/mol, more particularly 50to 2000 g/mol, and having 1 to 8, preferably 1 to 4, hydroxyl groups.

Preferred starters of the formula (3) used are those in which R¹ is ahydroxyl group or a saturated or unsaturated linear, branched or cyclicor further-substituted oxyorganic radical having 1 to 1500 carbon atoms,which if desired may also be interrupted by heteroatoms such as O, S, Sior N, or a radical comprising an oxyaromatic system; preferably R¹ is analkoxy, arylalkoxy or alkylarylalkoxy group and more particularly apolyether radical, in which the carbon chain may be interrupted byoxygen atoms, or a singly or multiply fused oxyaromatic group or anoptionally branched, silicone-containing organic radical.

Furthermore, R¹—H may represent an oxyalkyl-functional siloxane or anoxy-functional polyethersiloxane.

The chain length of the polyether radicals containing alkoxy, arylalkoxyor alkylarylalkoxy groups that can be used as a starter compound isarbitrary. The polyether, alkoxy, arylalkoxy or alkyarylalkoxy groupcontains preferably 1 to 1500 carbon atoms, more preferably 2 to 300carbon atoms, more particularly 2 to 100 carbon atoms.

The compounds of the formula (3) are preferably selected from the groupof the alcohols, polyetherols or phenols. As starter compound it ispreferred to use a monohydric or polyhydric polyether alcohol or alcoholR¹—H (the H belongs to the OH group of the alcohol or phenol) or elsewater.

As starter compounds (3) it is advantageous to use low molecular masspolyetherols having 1 to 8 hydroxyl groups and molar masses of 50 to2000 g/mol, which have in turn been prepared beforehand by DMC-catalyzedalkoxylation. Examples of compounds of the formula (3) include water,allyl alcohol, butanol, octanol, dodecanol, stearyl alcohol,2-ethylhexanol, cyclohexanol, benzyl alcohol, ethylene glycol, propyleneglycol, di-, tri- and polyethylene glycol, 1,2-propylene glycol, di- andpolypropylene glycol, 1,4-butanediol, 1,6-hexanediol,trimethylolpropane, glycerol, pentaerythritol, sorbitol, cellulosesugars, lignin or else other hydroxyl-bearing compounds based on naturalsubstances.

Suitability is possessed, besides compounds having aliphatic andcycloaliphatic OH groups, by any compounds having 1 to 20 phenolic OHfunctions. These include, for example, phenol, alkylphenols andarylphenols, bisphenol A and novolaks.

The compounds thus prepared provide the freedom in synthesis to choosebetween polyoxyalkylene compounds containing alkoxysilyl groups thatcontain the alkoxysilyl functions either terminally, or in isolation, inblockwise cumulation, or else scattered statistically into thepolyoxyalkylene chain.

A feature of the silyl polyethers 1 of the formula (2) is that in termsof construction and molar mass they can be prepared targetedly andreproducibly. The sequence of the monomer units can be varied withinwide limits. Epoxide monomers may be incorporated into the polymer chainas desired, in blockwise sequence or randomly. The fragments insertedinto the polymer chain that forms, as a result of the reaction involvingring opening of the reaction components, are freely permutible betweenone another in terms of their sequence, subject to the restriction thatcyclic anhydrides and also carbon dioxide are present in randominsertion, in other words not in homologous blocks, in the polyetherstructure.

Silyl polyethers of the formula (2) are composed of alkoxysilyl groupsubstituted chains which, as a result of the choice of the fragments dto j, corresponding to the fragments inserted into the polymer chain asa result of the reaction involving ring opening of the reactioncomponents, are specifically highly functionalized and can therefore betailored for different kinds of fields of application.

The index numbers given in the formulae set out here, and the valueranges of the indices specified, are therefore to be understood as theaverage values of the possible statistical distribution of thestructures and/or mixtures thereof that are actually present. The sameapplies to structural formulae which per se are reproduced exactly, suchas, for example, to formula (2) and/or (3).

Depending on the epoxide-functional alkoxysilane and any furthermonomers employed, and also, possibly, carbon dioxide, it is possiblefor ester-modified or carbonate-modified silyl polyethers to beobtained. The alkoxysilyl unit in the compound of the formula (2) ispreferably a trialkoxysilyl unit.

As shown by ²⁹Si-NMR and GPC investigations, the process-relatedpresence of OH groups in chain-end positions provides the possibilityfor transesterification reactions on the silicon atom not only duringthe DMC-catalyzed preparation but also, for example, in a downstreamoperating step. In such reactions, formally, the alkyl radical Rattached to the silicon by an oxygen atom is replaced by a long-chainmodified alkoxysilyl polymer radical. Bimodal and multimodal GPC curvesdemonstrate that the alkoxylation products include not only theuntransesterified species, as shown in formula (2), but also thosehaving twice, in some cases three times, or even four times the molarmass. Formula (2), accordingly, shows only a simplified version of thecomplex chemical reality.

The silyl polyethers 1, accordingly, represent compositions which alsocomprise compounds in which the sum of the indices (a) plus (b) informula (2) is on average less than 3, since some of the OR groups maybe replaced by silyl polyether groups. The compositions thus comprisespecies which are formed on the silicon atom, with elimination of R—OHand condensation reaction with the reactive OH group of a furthermolecule of the formula (2). This reaction may take place a number oftimes, until, for example, all of the RO groups on the silicon have beenreplaced by further molecules of the formula (2). The presence of morethan one signal in typical ²⁹Si-NMR spectra of these compoundsunderlines the occurrence of silyl groups with different substitutionpatterns.

The values and ranges of preference that are specified for the indices(a) to (j) are therefore also to be understood only as average valuesover the different, individually undeterminable species. The diversityof chemical structures and molar masses is also reflected in the broadmolar mass distributions that are typical of silyl polyethers 1 and areentirely unusual for conventional DMC-based polyethers, vis molar massdistributions M_(w)/M_(n) of usually ≧1.5.

In the case of the prior-art methods, only silyl-group-terminatedprepolymers can be formed. The silyl polyethers 1 used as a reactivecomponent differ from oligomers or polymers modified by conventionalmethods in that, as a result of the deliberate chain construction andthe variable insertion of functional groups in both blocklike andisolated manner, structures are formed which on the one hand have silylfunctionalization scattered or distributed in blocks across the entirechain, while, on the other hand, may—but need not necessarily—carrysilyl functionalization at the ends as well.

Inseparably connected with the process for alkoxylating epoxy-functionalalkoxysilanes that is set out in the as yet unpublished specification DE10 2008 000360.3 is the feature that at the ends there is always an OHfunctionality present, originating from the epoxide ring opening of thelast epoxide monomer in each case, with attachment to the OH-functionalend of the growing chain. It is this same terminal OH functionality ofthe silyl polyethers, used here as a reactive component, that opens theway for their further functionalization with compounds containingisocyanate groups, with formation of a urethane linkage.

Suitable isocyanate-group-containing compounds include all knownisocyanates. Preference in the sense of the teaching according to theinvention is possessed, for example, by aromatic, aliphatic andcycloaliphatic polyisocyanates having a number-average molar mass ofbelow 800 g/mol. Suitable examples thus include diisocyanates from theseries consisting of 2,4-/2,6-toluene diisocyanate (TDI), methyldiphenyldiisocyanate (MDI), triisocyanatononane (TIN), naphthyl diisocyanate(NDI), 4,4′-diisocyanatodicyclohexylmethane,3-isocyanatomethyl-3,3,5-trimethylcyclohexyl isocyanate (isophoronediisocyanate=IPDI), tetramethylene diisocyanate, hexamethylenediisocyanate (HDI), 2-methylpentamethylene diisocyanate,2,2,4-trimethylhexamethylene diisocyanate (THDI), dodecamethylenediisocyanate, 1,4-diisocyanatocyclohexane,4,4′-diisocyanato-3,3′-dimethyldicyclohexylmethane,2,2-bis(4-isocyanatocyclohexyl)propane,3-isocyanatomethyl-1-methyl-1-isocyanatocyclohexane (MCI),1,3-diisooctylcyanato-4-methylcyclohexane,1,3-diisocyanato-2-methylcyclohexane and α,α,α′,α′-tetramethyl-m- or-p-xylylene diisocyanate (TMXDI), and also mixtures of these compounds.

Preferred starting materials for the preparation of the compoundscontaining urethane groups are hexamethylene diisocyanate (HDI),isophorone diisocyanate (IPDI) and/or4,4′-diisocyanatodicyclohexylmethane.

Likewise suitable as isocyanate-containing starting components arereaction products of the aforementioned isocyanates with themselves orwith one another to form uretidiones or isocyanurates. Examples includeDesmodur® N3300, Desmodur® N3400 or Desmodur® N3600 (all BayerMaterialScience, Leverkusen, Del.).

Also suitable, in addition, are derivatives of isocyanates, such asallophanates or biurets. Examples include Desmodur® N100, Desmodur®N75MPA/BA or Desmodur® VPLS2102 (all Bayer MaterialScience, Leverkusen,Del.). Where polyisocyanates of this kind are reacted with silylpolyethers having more than one reactive OH group in the molecule,linear or branched copolymers are formed in which the silyl polyetherfragments and isocyanate fragments are linked with one another inalternation via urethane groups. Where the isocyanate component is usedin a molar excess over the silyl polyether component, the products arereactive prepolymers which terminally carry NCO groups and haveadditional alkoxysilyl functionality. Through ongoing reaction on theurethane groups with isocyanates it is possible, furthermore, toconstruct allophanate structures and to build additional branches intothe backbone of the prepolymers.

Where, in the other case, the silyl polyether 1 is used in excess,urethanized polyols are formed which carry alkoxysilyl groups and haveterminal OH groups.

The silyl polyethers 1 can also be modified with monofunctionalisocyanates. In the simplest case, alkyl, aryl and/or arylalkylisocyanates are reacted with the OH groups of the silyl polyether,forming the respective adduct and at the same time endcapping thereactive chain end of the silyl polyether employed. Suitability for thispurpose is possessed, for example, by methyl, ethyl, butyl, hexyl,octyl, dodecyl and stearyl isocyanate. Particularly suitablemonofunctional isocyanates are those which in turn carry crosslinkablealkoxysilyl groups in the molecule. They include, preferably,isocyanatoalkyltrialkoxysilanes and isocyanatoalkylalkyldialkoxysilanes.

Alkoxysilane-functional monoisocyanates which can be used includeisocyanatotrimethoxysilane, isocyanatomethyltriethoxysilane,(isocyanatomethyl)methyldimethoxysilane,(isocyanatomethyl)methyldiethoxysilane,3-isocyanatopropyltrimethoxysilane,3-isocyanatopropylmethyl-dimethoxysilane,3-isocyanatopropyltriethoxysilane and3-isocyanatopropylmethyldiethoxysilane. Preference here is given to theuse of 3-isocyanatopropyltrimethoxysilane and -triethoxysilane.

By this chemical pathway it is possible to obtain modified silylpolyethers which are endowed terminally by one additional alkoxysilylgroup in each case. The reaction of alkoxysilane-functionalmonoisocyanates has been known to date only for conventionalOH-functional polymers such as polyethers which themselves contain noalkoxysilyl groups. Processes and products of this kind are describedin, for example, the publications below.

For the skilled person it is completely surprising that the curableprepolymers containing urethane groups that are present in the curablematerials of the invention have considerably lower viscosities in directcomparison with prior-art compounds of analogous molecular weight, asare disclosed, for example, for the Desmoseal® products in a brochurefrom Bayer MaterialScience having the title “Prepolymers: Products andApplications”, Reported therein are viscosities of 35 000 mPas.

The adhesives and sealants, binders and modifiers of the invention maybe modified chemically by follow-on reactions on the NCO and/oralkoxysilyl functions, as for example by reaction with monofunctional orpolyfunctional alcohols, such as methanol, ethanol, butanol, glycerol,trimethylolpropane, 2-ethylhexyl alcohol or fluorinated alcohols, suchas 2,2,2-trifluoroethanol, or acrylated alcohols, such as hydroxyethylacrylate, hydroxypropyl acrylate or hydroxybutyl acrylate, orpolyetherdiols or polyesterdiols or polytetrahydrofuran, and also byreactions with silicone polyether copolymers which have OH-functionalpolyether radicals, amino-functional polymers such as polyethers andpolysiloxanes, or 3-aminopropyltrialkoxysilanes, generally amines,alkoxysilanes, organic acid chlorides, organofluorine compounds, etc.,in order to produce or reinforce particular properties of the curableprepolymer. In this way it is possible if desired to introduce furtherfunctional groups into the molecule.

Also possible by this means is the targeted influencing of the molarmass and/or viscosity of the products. Hence it is possible to realizeaverage molar masses within a wide range from 500 g/mol to more than 100000 g/mol.

The urethane-group-containing adhesives, sealants, binders and modifiersof the invention are prepared by reaction of one or more isocyanateswith one or more silyl polyethers 1. In the preparation process, some orall of the OH functions of the silyl polyethers 1 are reacted withisocyanate groups, producing—according to starting material andstochiometry—optionally OH-functional or NCO-functional or terminallycapped, urethanized curable prepolymers. Dual-cure systems as well canbe obtained in this way, which can be cured simultaneously or insuccession by crosslinking reactions on the two types of reactivegroups.

It may be necessary to bear in mind that some of the NCO functions arereacted through side reactions, as in the formation of allophanates, forexample.

The curable materials of the invention comprising urethanized andsilylated polymers may comprise further components that carry reactivegroups. Such components include all compounds having at least oneisocyanate, hydroxyl, amino, epoxy and unsaturated C═C group, such asacrylates, methacrylates, vinyl compounds and allyl compounds, forexample.

On the basis of their hydrolysis-sensitive and readily crosslinkingalkoxysilyl and optionally isocyanate groups, the adhesives, sealants,binders and modifiers of the invention constitute curable polymers.Their crosslinking to solid end products is accomplished in a simple wayin the presence of water and, optionally, with addition of acid or baseas accelerant, the pot life being controllable by an increase intemperature during the curing procedure. The polymer construction ofthese crosslinkable urethane polymers can be varied in a multitude ofways in order to tailor performance properties in the product to theparticular end use. Hence it is possible, by varying the fraction ofalkoxysilane units in the polymer chain, to influence the crosslinkingdensity and hence the mechanical and physicochemical profile ofproperties of the cured polymers within wide boundaries. Here,surprisingly, even products equipped with a considerable density ofalkoxysilyl functionalization are generally liquids which are easy tohandle, and so, even in the case where highly crosslinked, well-adheringadhesive bonds are aimed for, there are no restrictions at all on theapplication of these components. This observation distinguishes theteaching of the invention from the procedure set out in DE 10 2006 054155 (US 2010-0078117), which is based on the introduction of free silanemonomers as formulating constituents into the end formulas, in order toensure that the necessary crosslinking density is achieved inconjunction with low processing viscosity. The curable urethanizedpolymers containing alkoxysilyl groups, which are subject to virtuallyno limits in terms of their structural diversity, open up a path to theskilled polymer chemist, through the incorporation, for example, ofester, carbonate and aromatic structural elements in the silyl polyether1 and through the variation of the isocyanate component, to a designfreedom which addresses virtually any performance needs.

As the skilled person is aware, the crosslinking or curing ofalkoxysilyl groups takes place in a two-stage chemical process in which,in a first step, in the presence of water—atmospheric moisture may alsosuffice—the alkoxy groups attached to the silicon are eliminated in theform of corresponding alcohols, and SiOH groups are formed. The lattercondense in the case of self-condensation subsequently, with formationof Si—O—Si bridges with one another, and form polymeric materials.Alternatively the SiOH-functional intermediates react with substratescontaining reactive groups—for example, they react particularly wellwith OH-functional silicatic surfaces—and lead to excellent chemicalanchoring on the substrate in question. The rate of cure can beinfluenced in a diversity of ways through addition of catalysts orthrough temperature variation. Where the silane prepolymer additionallycontains NCO groups, the possibility exists for the curing thereof inthe presence, for example, of OH-functional compounds such as water,alcohols, diols, polyols, polyetherols, aromatic hydroxyl compoundsand/or amines, diamines, polyamines.

As a further reactive component it is possible to use amines, which onthe one hand may participate in curing, with formation of urea groups,and on the other hand may have a catalytic effect in relation to thecrosslinking of the alkoxysilyl groups.

As catalysts for the crosslinking and/or curing and also for thechemical fixing of the alkoxysilyl prepolymers bearing urethane groupson particle surfaces and macroscopic surfaces it is possible to use theknown polyurethanization, allophanatization or biuretization catalysts,which are known per se to the skilled person, and/or the catalysts thatare known from the literature and are commonly used for the hydrolysisand condensation of alkoxysilanes. They include compounds such as, forexample, the zinc salts zinc octoate, zinc acetylacetonate and zinc(II)ethylcaproate, or tetraalkylammonium compounds, such asN,N,N-trimethyl-N-2-hydroxypropylammonium hydroxide,N,N,N-trimethyl-N-2-hydroxypropylammonium-2-ethylhexanoate or choline2-ethylhexanoate. Preference is given to using zinc octoate (zinc(II)ethylhexanoate) and the tetraalkylammonium compounds, more preferably tousing zinc octoate. It is additionally possible as catalysts to use theorganotin compounds that are commonly employed, such as dibutyltindilaurate, dioctyltin dilaurate, dibutyltin diacetylacetonate,dibutyltin diacetate or dibutyltin dioctoate, etc., for example.Furthermore, it is also possible for bismuth catalysts, an example beingthe Bor-chi catalyst, titanium compounds, e.g. titanium(IV) isopropylateor titanyl acetylacetonate, iron(III) compounds, e.g. iron(III)acetylacetonate, aluminium compounds, such as aluminium triisopropylate,aluminium tri-sec-butylate and other alcoholates, and also aluminiumacetylacetonate, calcium compounds, such as calcium disodiumethylenediaminetetraacetate or calcium diacetylacetonate, or elseamines, e.g. triethylamine, tributylamine,1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]undec-7-ene,1,5-diazabicyclo[4.3.0]non-5-ene,N,N-bis-(N,N-dimethyl-2-aminoethyl)methylamine,N,N-dimethylcyclohexylamine, N,N-dimethylphenylamine, N-ethylmorpholineetc., to be used. Organic or inorganic Brønsted acids as well, such asacetic acid, trifluoroacetic acid, methanesulphonic acid,p-toluenesulphonic acid or benzoyl chloride, hydrochloric acid,phosphoric acid, the monoesters and/or diesters thereof, such as butylphosphate, (iso)propyl phosphate, dibutyl phosphate etc., are suitablecatalysts. It is of course also possible to use combinations of two ormore catalysts.

The modifiers and compositions of the invention may also comprise whatare called photolatent bases as catalysts, as described in WO2005/100482. Photolatent bases are preferably organic bases having oneor more basic nitrogen atoms, which initially are present in a blockedform and release the basic form through splitting of the molecule onlyafter irradiation with UV light, visible light or IR radiation.

The catalyst or photolatent base is employed in amounts of 0.001% to10.0% by weight, preferably 0.01% to 1.0% by weight and more preferably0.05% to 0.5% by weight, based on the modifiers. The catalyst orphotolatent base may be added in one portion or else in a plurality ofportions or else continuously. It is preferred to add the entire amountin one portion.

Furthermore, the adhesives and sealants, binders and modifiers of theinvention may comprise other reactive silanes, preferably alkoxysilanes.

These alkoxysilanes may be both monomeric silanes such as those of theformula (4) and also polymer-bonded silanes,U_(x)SiV_((4-x))  (4)where U represents identical or different groups which arenon-hydrolysable in the presence of water and catalytic amounts ofBrønsted acid at temperatures of up to 100° C., V represents identicalor different groups which are hydrolysable in the presence of water andcatalytic amounts of Brønsted acid at temperatures up to 100° C., orhydroxyl groups, and x is 1, 2, 3 or 4.

Hydrolysable in the context of this invention means that at least 80% ofthe groups can be hydrolysed and hence eliminated under the conditionschosen.

The alkyl chain may have 0 to 50, preferably 0 to 22, carbon atoms andmay also be interrupted by heteroatoms such as oxygen or nitrogen orsulphur or else may be a silicone radical. The aromatic radical may alsobe heteroaromatic. The radicals A and B may possibly have one or morecustomary constituents, such as halogen or alkoxy, for example.

Non-hydrolysable radicals U according to the formula (4) with functionalgroups may be selected from the area of the glycidyl orglycidyloxyalkylene radicals, such as, for example, β-glycidyloxyethyl,γ-glycidyloxypropyl, δ-glycidyloxypropyl, ε-glycidyloxypentyl,ω-glycidyloxyhexyl or 2-(3,4-epoxycyclohexyl)ethyl, themethacryloyloxyalkylene and acryloyloxyalkylene radicals, such as, forexample, methacryloyloxymethyl, acryloyloxymethyl, methacryloyloxyethyl,acryloyloxyethyl, methacryloyloxypropyl, acryloyloxypropyl,methacryloyloxybutyl or acryloyloxybutyl, and the 3-isocyanatopropylradical, and/or cyclic and/or linear (poly) urethane-group-containingand/or urea-containing and/or (poly)amino-group-containing radicals.

Particularly widespread is the use of low-viscosity, monomeric compoundswhich carry trimethoxysilyl and triethoxysilyl groups and which, in thepresence of atmospheric moisture and suitable catalysts, usually even atroom temperature, are capable of undergoing condensation withelimination of the alkoxy groups and formation of Si—O—Si bonds with oneanother. Organofunctional monomeric silanes of this kind are, forexample, N-cyclohexylaminomethyltrimethoxysilane,N-cyclohexyl-3-aminopropyltriethoxysilane,3-aminopropyltrimethoxysilane, vinyltrimethoxysilane,vinyltriethoxysilane, vinyldimethoxymethylsilane,3-isocyanatopropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane,3-glycidyloxypropyltriethoxysilane,3-methacryloyloxypropyltrimethoxysilane, methyltrimethoxysilane,methyltriethoxysilane, dimethyldimethoxysilane, phenyltriethoxysilaneand hexadecyltrimethoxysilane. The methodology is essentially known tothe skilled person.

The silylated polymers containing urethane groups can likewise beemployed in mixtures with all silyl-functional compounds which have atleast one alkoxysilyl group attached chemically to a polymer backbone.

Silane-modified polymers of this kind are silane compounds of the typeof the formula (5)

where

-   X¹, X² and X³ independently of one another are alkyl or alkoxy    radicals having 1-8 C atoms,-   A represents a carboxyl, carbamate, amide, carbonate, ureido or    sulphonate group containing radical or denotes an oxygen atom,-   w is an integer from 1 to 8 and-   v is an integer from 1 to 20, preferably 1 to 15 and more    particularly 1 to 5.

The polymer radical is selected from a group consisting of alkyd resins,oil-modified alkyd resins, saturated or unsaturated polyesters, naturaloils, epoxides, polyamides, polycarbonates, polyethylenes,polypropylenes, polybutylenes, polystyrenes, ethylenepropylenecopolymers, (meth)acrylates, (meth)acrylamides and salts thereof,phenolic resins, polyoxymethylene homopolymers and copolymers,polyurethanes, polysulphones, polysulphide rubbers, nitrocelluloses,vinyl butyrates, vinyl polymers, ethylcelluloses, cellulose acetatesand/or butyrates, rayon, shellac, waxes, ethylene copolymers, organicrubbers, polysiloxanes, polyethersiloxanes, silicone resins, polyethers,polyether esters and/or polyether carbonates.

The polymers of the formula (5) that are used preferably in mixtureswith the silyl polymers containing urethane groups include what arecalled α-silane-terminated polymers, whose reactive alkoxysilyl group isseparated only by one methylene unit (v=1) from a nitrogen-containing,polymer-bonded group A, as described in WO 2005/100482 and EP-A1-1 967550 (US 2009-0088523).

Other silane polymers of the formula (5) which can be used in accordancewith the invention in curable compositions are those in which the silanegroup is attached terminally via a propylene unit (v=3) to a polymerbackbone, and in which A represents a urethane group. Preference isgiven here to polyalkylene oxides, especially polypropylene glycols(w=2), having silane functions on each of the two chain ends, asdescribed in EP-A1-1 824 904 (US 2009-0264612).

Compounds of the formula (5) that are also suitable as mixtureconstituents are silane-terminated polyurethanes whose preparation froma polyol by reaction with a diisocyanate and subsequently with anamino-functional alkoxysilane is described in, for example, U.S. Pat.No. 7,365,145, U.S. Pat. No. 3,627,722 or U.S. Pat. No. 3,632,557. Thelinking group A in this case is a radical which carries urethane andurea groups. Other polymers which can be used for the purposes of theinvention are urethane-free and urea-free silyl-terminated polyethers ofthe formula (5) where A is oxygen, in which the terminal alkoxysilylgroups are attached directly to the polymer backbone via an etherfunction. Silyl polymers of this kind are described in U.S. Pat. No.3,971,751. They are composed preferably of a polyether backbone where vin formula (5) has a value of preferably 3 and w has a value ofpreferably 2, and are available as MS Polymer® products from Kaneka.

Polysiloxanes which carry alkoxysilyl groups as well, as described in WO2007/061847 (US 2008-0306208), for example, can be combined with theurethanized and silylated polymers of the invention.

The invention provides for the use of the curable materials comprisingthe urethane-group-containing alkoxysilyl prepolymers and, optionally,at least one further alkoxysilane component of formula (4) or (5) asadhesives, sealants, binders or modifiers.

Furthermore, the curable mixtures may comprise one or more isocyanate,hydroxyl and/or amine compounds.

Generally it is left up to the expert to select the components that aresuitable for the desired profile of properties, in order to producecopolymer systems with optimum adaptation. Through the compositionsaccording to the invention, accordingly, a construction kit of differentprofiles of properties is available, from which an optimized selectioncan be made in order to match the application.

The inventive introduction of urethane groups into the prepolymerstructure allows the known properties of the pure polyurethanes,including good adhesion properties on different substrates, highresistance to solvents, chemicals and effects of weathering, and theirhigh mechanical flexibility, to be combined with the advantages ofcurable silyl polyethers.

Here, surprisingly, even urethanized silyl polyether isocyanate adductsequipped with a considerable density of alkoxysilyl functionalizationare generally low-viscosity liquids which are easy to handle, and so,even in the case where highly crosslinked, well-adhering adhesive bondsare aimed for, there are no restrictions at all on the metering of thiscomponent. This observation distinguishes the teaching of the inventionfrom the procedure set out in WO 2008/058955 (US 2010-0078117), which isbased on the introduction of free silane monomers as formulatingconstituents into the end formulas, in order to ensure that thenecessary crosslinking density is achieved in conjunction with lowprocessing viscosity. The prepolymers containing alkoxysilyl groups,which are subject to virtually no limits in terms of their structuraldiversity, open up a path to the skilled polymer chemist, through theincorporation, for example, of ester, carbonate and aromatic structuralelements, to a design freedom already which addresses virtually anyperformance needs.

The curable material and prepolymers obtained by the process of theinvention, and also the compositions comprising them, are suitable asbase materials for the production of a multiplicity of industriallyapplicable products.

The invention therefore further provides for the use of theurethane-group-containing curable compositions, for preparing or as, forexample, adhesives, sealants, sealing compounds, binders,surface-coating materials, reactive crosslinkers, adhesion promoters,water repellents, wetting agents, primers and/or surface modifiers,architectural water repellents, additives in lacquer formulations ornail varnish formulations.

The curable materials are suitable for a very wide variety ofmacroscopic or microscopic substrates, selected, for example, from thefollowing group: metals and/or metal oxides, glass and glassfibres/glass fabrics, wood, wood-based materials, natural fibres, andalso, for example, cork and/or, generally, silicatic materials,concrete, mortar, plaster, masonry, and/or particles, oxidic particles,fumed silica, precipitated silicas, quartz particles and other inorganicoxide particles, glass particles, titanium dioxide, aluminium oxide,zirconium dioxide, cerium dioxide, iron oxides, copper oxides, kaolin,wollastonite, talc, mica, feldspars, hydroxides, aluminium trihydroxide,magnesium dihydroxide, boehmite, hydrotalcite and hydroxydic ironpigments, FeO(OH), carbonates, calcium carbonate and/or dolomite, iron,copper, zinc, nickel, aluminium, magnesium, metal alloys and/orcarbon-containing materials, graphite and/or carbon black, organicparticulate substrates, silicone resins, organically modified silicones,organic polymers and/or biopolymers, leather, tissue, paper and/ormixtures thereof.

Thus the targeted installation of the alkoxysilyl moities which anchorthemselves via hydrolytic processes to masonry, concrete, mortar, etc.proves to be extremely advantageous when systems equipped in this wayare employed in the area of the construction industry, in applicationsinvolving the joining and insulating sealing of, for example frames forwindows and doors in construction shells.

The curable materials of the invention and also the compositionscomprising them can be used in the form of solutions or else emulsionsor suspensions or foams. The solvent or suspension/emulsion medium maybe selected according to the application. As well as water, suitabilityis possessed by aromatic and nonaromatic solvents, including alcohols,hydrocarbons, etc.

In the context of increasing environmental awareness, however, theaddition of organic solvents for the purpose of reducing the viscosityof surface-modifying formulations has in recent years come increasinglyunder fire. An alternative option is to apply theurethane-group-containing silyl polyethers in the form of an aqueousemulsion.

A further use of the urethanized curable materials bearing alkoxysilylgroups is as aqueous emulsions, prepared by the process disclosed in theas yet unpublished specification DE 10 2009 022630.3. In spite of thesupposed and structurally determined sensitivity of the reactiveprepolymers to hydrolysis, it has now been found, surprisingly, thatthey can be converted into stable emulsions. An emulsion is termedstable when the emulsion, preferably after one month of storage at roomtemperature, but at least after one week of storage at room temperature,shows no signs visible to the eye of breaking. The breaking of anemulsion is defined here as its separation into a macroscopic oil phaseand water phase. An emulsion is termed stable to hydrolysis if after onemonth of storage at room temperature, but at least after one week ofstorage at room temperature, the free alcohol content of the emulsioncorresponds to the splitting of not more than 10% by weight of theemulsified alkoxysilyl groups.

The optimum mass fraction of water and of polymer is dependent on theapplication. It is left to the skilled person to find the optimum massfraction of the reactive polymer for a particular area of application.The skilled person, however, is familiar with the fact that thepreferred fraction of water in such emulsions lies between 10% by weightto 97% by weight, more preferably between 20% by weight and 90% byweight, and more particularly greater than 30% by weight.

Suitable emulsifiers for such emulsions include in principle allanionic, nonionic, cationic and amphoteric emulsifiers and alsoemulsifier mixtures. Preferred examples of such emulsifiers are alcoholethoxylates, fatty acid ethoxylates, ethoxylated esters, and(ethoxylated) sorbitan esters.

The aqueous phase of the emulsions may comprise hydrophilic, inorganicfillers for modifying the mechanical properties of the coatings of theinvention, with the proviso that these hydrophilic fillers are addedsubsequently to the already stabilized emulsion. It can be advantageousif the surface of the fillers used has at least one functional group, sothat, after drying and/or breaking of the emulsion, there are chemicalreactions between reactive functional groups of theurethane-group-containing silyl polyether with those on the fillersurface. Examples of such fillers are fumed and precipitated silica,inorganic oxides such as aluminium oxide, titanium dioxide and zirconiumdioxide, glass and quartz, hydroxides such as aluminum hydroxide andmagnesium hydroxide, silicates such as wollastonite, mica, kaolin andtalc, calcium carbonate and other carbonates, metals such as copper,zinc and nickel, and metal alloys, and also graphite and carbon black.

The emulsion may further comprise low-molecular-mass, organofunctionaland water-insoluble silanes, as described above. The emulsion maylikewise comprise catalysts for fixing the urethane-group-containingsilyl polyethers to a surface.

It is also possible for other functional substances to be added to theemulsions. Such substances include, for example, rheological additives,defoamers, deaerating agents, film-forming polymers, antimicrobial andpreservative substances, antioxidants, dyes, colorants and pigments,anti-freeze agents, fungicides, adhesion promoters and/or reactivediluents, and also plasticizers and complexing agents. Additionally,spraying assistants, wetting agents, vitamins, growth substances,hormones, fragrances, light stabilizers, free-radical scavengers, UVabsorbers and other stabilizers may be added to the mixtures.

The invention further provides for the use of emulsions and/orsuspensions comprising the curable materials of the invention, where theemulsions and/or suspensions comprise compounds selected from the groupsof catalysts, photolatent bases, additives for modifying the rheologicalproperties, hydrophilic fillers, organofunctional and/or partiallysoluble and/or water-insoluble silanes and/or siloxanes, auxiliaries,film formers, antimicrobial and preservative substances, dispersants,defoamers and deaerating agents, dyes, colorants and pigments,anti-freeze agents, fungicides, adhesion promoters and/or reactivediluents, plasticizers and complexing agents, spraying assistants,wetting agents, vitamins, growth substances, hormones and/or fragrances,light stabilizers, free-radical scavengers, UV absorbers and/orstabilizers.

The invention further provides for the use of the curable materialsand/or of the emulsions and/or suspensions as base materials forvarnishes, inks, release agents, adhesives, cosmetic products,scratch-resistant coatings, architectural preservatives, corrosioninhibitors and/or sealants, for coating paper, particles, textile fibresand glass fibres, for coating fillers for paper, for generatingantistatic surfaces and/or as starting material for the production ofrubber parts on the basis of polypropylene oxide.

The curable materials of the invention can be employed as binders, inother words for the joining of materials of the same or different kindsto one another. The materials to be bonded, or to be joined to oneanother, may be, for example, glass, metals, plastics, wood or buildingmaterials such as concrete, linker, ceramic or stone. In the productionof wood-based materials, such as chipboard, OSB or MDF boards, forexample, they serve for the bonding of the wood particles or corkparticles (including wood chips or wood fibres) and hence are alsoavailable for flooring, including wood-block flooring, and laminateapplications as a substitute for amino resins or isocyanate bondingcompositions.

The curable materials of the invention may also possess thermoplasticproperties and hence may also serve for producing mouldings for which atemperature-dependent flow behaviour is required. The moulding compoundsmay be used in processes such as, for example, injection moulding,extrusion or hot pressing. The polymers of the invention may be usedpreferably without catalysts, thus preventing further crosslinking andcuring during the shaping operation. Following crosslinking, thepolymers carrying silyl groups and optionally NCO groups undergoconversion to form thermoset products.

The curable materials of the invention find application likewise in thepolyurethanes sector. Depending on whether they have terminal hydroxylgroups or isocyanate groups, they may take on the function of the polyolcomponent and/or isocyanate component in polyurethane systems that areknown to the skilled person. In systems of this kind, the prepolymersequipped with moisture-crosslinking alkoxysilyl groups are usedpreferably in a mixture with other conventional polyols and/orisocyanate compounds. The use of alkoxysilyl-bearing components of thiskind in PU systems permits the reactive attachment of the polyurethanesand polyurethane foams produced to a variety of substrate surfaces.

The invention therefore provides curable materials produced by reactingat least one silyl polyether 1 with at least one isocyanate compound asa constituent of compositions which can be used as adhesives, bondingmaterials and/or coating materials, including as a component inpolyurethane systems.

The surfaces to be coated can be coated by known methods such asspraying, spreading, dipping, etc. The surfaces to be bonded arepreferably pressed together in the course of the process. Theapplication of the optionally foamable mixture (compositions) in orderto produce the adhesive bond takes place preferably from a pressurizedcan, with foam formation taking place by means of the blowing agentwhich is present in the mixture and may also be released by chemicalreaction.

When the surfaces to be bonded are pressed together, the structure ofthe foam is preferably at least largely destroyed. Accordingly, thefoam, when it has been pressed between surfaces to be bonded, has a gasbubble content of preferably less than 60% of its volume, morepreferably less than 40% of its volume, and with particular preferenceless than 20% of its volume.

In one preferred embodiment, at least one of the surfaces to be joinedis moistened before the inventive application of the foam. With veryparticular preference, one of the surfaces to be joined is moistened,while the foam is applied to the other surface. The foam is then pressedbetween the two surfaces.

The high initial strength of this foam can be attributed to a phenomenonwhich is surprising even to the skilled person. Hence, in contrast towhat is the case with conventional silane-crosslinking adhesives, thebond strength of the foam is developed not only as a result of thechemical silane crosslinking. Instead, alongside this chemical curingprocess, there is also a remarkable physical effect apparent, as knownotherwise only in contact adhesives, where the development of strengthtakes place only through the evaporation of added solvents. In the caseof the foam, the function of these solvents is taken over by the blowingagent or blowing agent mixture. In contrast to what is the case with thecontact adhesives, which cure only very slowly, the blowing agents,instead of unhurried evaporation, evaporate in large part suddenly evenwhile the foamable mixture is being foamed. They foam up to form thefoam, which, in spite of the very high viscosity following evaporationof the blowing agent, remains—surprisingly—highly mobile, so that thefoam can be collapsed without problems by the pressing-together of thesurfaces to be bonded. When the foam is compressed, a thin, uniformlayer of adhesive is formed between the surfaces to be bonded, and thesurfaces are well wetted, thus allowing an optimum bonding effect to beachieved. This effect is subsequently reinforced by the chemical curingreactions that take place.

The invention accordingly further provides a method of adhesivelybonding surfaces, wherein a foamable curable material is provided whichis foamed between the surfaces to be bonded to form a foam, or else thefoam which is preparable from the mixture is applied, after foaming, toone of the surfaces to be bonded, or between the surfaces to be bonded,and the foam is subsequently compressed between the surfaces to bebonded.

The invention further provides a method of joining surfaces, in whichthe curable material is applied to at least one of the surfaces to bejoined or between the surfaces to be joined, which are then bonded withcuring.

The invention additionally provides an analogous method for the sealingor bridging or filling of surfaces, cracks or gaps, in which a curablematerial is applied between the surfaces to be sealed, which aresubsequently cured, with assurance of the imperviousness.

In both analogous methods, the curable material may be applied in theform of a foam.

Where these compositions of the invention are to be foamable, theycomprise one or more blowing agents which optionally are formedchemically and/or physically.

The invention therefore further provides for the curable materials whichcomprise one or more blowing agents, which may be formed chemicallyand/or physically, and the foams produced therewith.

The invention additionally provides a method of joining surfaces byapplying the curable material in the form of a foam.

The high initial bond strength of the foam is promoted by a very highfoam density. Hence it is possible to prepare foamable compositionswhich comprise

-   (A) the urethanized, silyl-group-bearing prepolymers and-   (B) less than 15% by weight of blowing agent, based on the total    mixture.

The mixture preferably contains less than 15% by weight of blowingagent, based on the total mixture.

Suitable blowing agents are gases which are condensable even atrelatively low pressures and which can also be used for producingsprayable assembly foams. Examples of common blowing agents includehydrocarbons having in each case 1 to 5, more particularly 3 to 5,carbon atoms, especially propane/butane mixtures or isobutane,hydrofluorocarbons having 1-5 carbon atoms, e.g.1,1,1,2-tetrafluoroethane or 1,1-difluoroethane, or dimethyl ether, andalso corresponding mixtures. The blowing agent content is preferably<10% by weight, more preferably <7% or <5% by weight, based on the totalmixture.

The blowing agent content, based on the total mixture, is preferably notmore than 10% by weight, more preferably not more than 7% by weight.

Foaming may also take place without addition of a blowing agent, on apurely chemical basis, then preferably, however, in the case of hotcuring or warm curing. In such cases, when the adhesive mixture isheated, a low-volatility blowing agent is formed which comprises, forexample, alcohols such as methanol or ethanol originating from thehydrolysis of the alkoxysilyl group. Water or an inert solvent may alsoserve at elevated temperature as blowing agents.

Where the coating of a substrate is desired, it is also possible toleave out the blowing agent, and to set the physical properties requiredfor coatings in a particular way, where appropriate by addition ofsolvents or other additives and auxiliaries.

The reactive urethanized and silane-functional curable materials arealso outstanding suitable for the modification of sheetlike and/orparticle surfaces.

Modification here refers to the chemical or physical attachment of amodifier to the solid surface in question. This modification, based onthe solid surface, may optionally be partial or complete, it beingpossible for the surface of the solid to be covered with an imperviousmonolayer or else with a multilayer. Modification in the sense of thisdefinition also includes surface coatings which in general cover thefull area, as in the case, for example, of paints, inks and/orhydrophobisizing agents.

Modifications of areas or particles for the purpose of modifyingsurfaces are carried out for a wide diversity of reasons and by a widevariety of methods, and are known to the skilled person from theliterature. Generally speaking, the purpose of modifications is toachieve a purposive adaptation of the chemical and physical propertiesof surfaces of a carrier material to the particular desired application,through the application to said surfaces of a layer—usually a thinlayer—of a modifier. For example, modifiers fulfil important functionsas adhesion promoters, primers, varnishes, water repellants or wettingagents. Common to all variants of the coatings is the application of alayer which adheres very well to the substrate in question, throughapplication of an often liquid or pulverulent, easy-to-apply modifier.This by no means ensures the purposive incorporation of silyl anchorgroups at those sites on the polymer that require their positive effect.

Depending on the nature of the surface to be modified, thechemicophysical nature of the modifier in question, and the performanceobjective of the desired surface modification, very different methodsare employed for applying the layers. In addition, for example, tothermal and electrochemical methods, chemical modification methods inparticular have a prominent role to play.

The effective adhesion to a wide variety of substrates is based on thehigh density of silane anchor groups, supported where appropriate byadditional reactions of NCO functions of the prepolymer with reactivegroups on the substrate surface, in combination with strong physicalinteractions of the urethane groups with polar chemical groups such asOH groups on the surface of the respective substrate. The absence offurther silyl groups in the structures of DE 10 2004 018548 within thebase polymer chain, in the form of side groups, for example, limits thecrosslinking density and also the adhesion after curing.

Crosslinking thereof to form solid end products, or chemical/physicalattachment thereof to reactive surfaces, as to particle surfaces, forexample, is accomplished in a simple way, optionally with the additionof water, acid or base or metal compounds as accelerants, the cure timebeing controllable through an increase in temperature during the curingoperation. The surfaces may by formed microscopically, in the form forexample of particles or particle agglomerates, and/or macroscopically,in the form of sheetlike structures or fibres or similarthree-dimensional bodies.

Particle surfaces of solid or else porous particles may besurface-coated in accordance with the invention by methods known fromthe prior art. These include the spraying of the urethanized silylpolyethers onto the particles with mixing, kneading and/or heating,optionally in the presence of suitable crosslinking catalysts. Themodifiers of the invention, purely or from suitable organic and/orinorganic solvents, may also be applied to the particle surfaces, wherethey are then able to react with covalent attachment. A furtherpossibility is to apply emulsions comprising the modifiers of theinvention in suitable media, where appropriate with addition ofauxiliaries, further modifiers and emulsifiers and/or wetting agents, tothe particle surfaces. Also possible is the modification of particlesurfaces in a matrix of (pre-)dispersed particles, as for example offunctional particles or particulate fillers (pre-)dispersed in a polymeror a paint, through addition of the modifiers to the correspondingsystems, with thorough mixing, where appropriate with heating and/or theaddition of a suitable catalyst. In each case, theurethane-group-containing silyl polyethers may be admixed with othercomponents, such as, for example, monomeric, oligomeric or polymericsilanes, or other components bearing reactive groups, and also materialswhich attach or cure by a different mechanism, such as, for example,acrylates, epoxides, isocyanates, carboxylates, hydroxides, lactones,lactams, etc. It is also possible to use mixtures with one another oftwo or more of the urethane-group-containing silyl polyethers.

The surfaces to be modified may be microscopic or macroscopic and maythus be composed of individual particles or aggregated particles.

The particles or substrates to be modified may be of a variety oforigins, sizes and particle-size distributions, and may also havedifferent morphologies (spherical, platelet-shaped (with differentaspect ratios) and fibrous, fractally aggregated, cubic or cuboidal,etc.), and may be in different states of agglomeration; such systemsinclude, for example, oxidic particles, such as fumed silica, examplesbeing AEROSIL®s from EVONIK Degussa GmbH, precipitated silicas, examplesbeing SIPERNAT®s from EVONIK Degussa GmbH, quartz particles and otherinorganic oxide particles, such as glass particles, titanium dioxide,such as, for example, AEROXIDE® TiO₂ P25 and AEROXIDE® TiO₂ P90 fromEVONIK Degussa GmbH, aluminium oxide, such as, for example, AEROXIDE®Alu C from EVONIK Degussa GmbH, zirconium dioxide and/or cerium dioxide,iron oxides, copper oxides, etc., silicatic particles such as, forexample, particles of kaolin, wollastonite, talc, mica, feldspars, etc.,hydroxides such as aluminium trihydroxide and/or magnesium dihydroxide,boehmite, hydrotalcite, silicatic materials in general, concrete,mortar, gypsum, masonry, oxidic particles, hydroxidic iron pigments,such as FeO(OH), carbonates, such as calcium carbonate and/or dolomite,metals such as iron, copper, zinc, nickel, aluminium, magnesium, etc.,metal alloys and/or carbon-containing materials, such as graphite and/orcarbon black, for example, etc.

As organic particulate substrates it is possible to use particlescomprising, for example, silicone resins, organically modifiedsilicones, organic polymers and/or biopolymers, etc.

The different particles may also be surface-modified in a mixture.

The ratio of particle material to curable material is dependent on theavailable particle surface area, the desired degree of modification andthe molecular weight of the modifying agent. Based on the mass of theparticles to be modified, the modifying agent or the curable material ofthe invention may be situated in terms of mass ratio of particlematerial:curable material in the range from 1:10 to 1 000 000:1,preferably from 1:1 to 10 000:1 and more preferably in the range from2:1 to 1000:1.

If the particle weight is viewed in relation to the total mixture usedfor surface modification, composed of compositions comprising thecurable material or materials or modifier or modifiers of the invention,optionally catalyst, solvents, further silane compounds, and also otherauxiliaries, then the mass ratio of particle weight:modifying mixturemay be situated in the range from 1:1000 to 100 000:1, preferably in therange from 1:100 to 1000:1, more preferably in the range of 2:1 to1000:1.

Macroscopic surfaces may also be coated with theurethane-group-containing silyl polyethers by the methods known from theprior art. In such cases the modifiers, either in pure form or else as ablend with further components, examples being inorganic and/or organicsolvents, reactive components such as monomeric, oligomeric or polymericsilanes, acrylates, epoxides, hydroxy compounds, amines, etc., and alsofurther coating components or auxiliaries, may be used for the surfacemodification.

The application of the urethane-group-containing silyl polyethers may inthis case take place in pure form purely, in organic or inorganicsolvents, as aqueous emulsions, as mixtures of theurethane-group-containing silyl polyethers with other compounds bearingsilyl groups, in combination with differently functionalized modifiers,such as isocyanates, hydroxyl compounds, epoxides, acrylates and amines,for example.

The modification of macroscopic surfaces with the materials describedmay be carried out, for example, by the methods known from the priorart, such as dip, spray or spin coating, flow coating, misting, brushapplication, rolling, printing, screen printing, stamping and—given asuitable consistency of the formulas of the invention that are used forsurface modification—by powder coating methods as well. Moreover, it isalso possible to use emulsions comprising the urethane-group-containingsilyl polyethers in suitable organic and/or inorganic solvents, whereappropriate with addition of further substances such as, for example,coating components, auxiliaries, such as, for example, wetting agents,emulsifiers and/or rheological additives, and also fillers and/orfunctional particles, for modifying the surfaces.

Examples of such surfaces are macroscopic and microscopic surfaces suchas surfaces of glass, paints, metals, semiconductor materials, oxidicmaterials such as stone, concrete or mortar, wood, organic and inorganicfibres, woven fabrics and particles, polymers, biopolymers, cork,leather, paper, tissue, etc.

The application possibilities for thus-modified surfaces or particlesurfaces are diverse. Thus, for example, particles treated in this waymay be used as fillers for polymers or for preparing polymer compounds,nanocomposites and master batches. The use of the urethane-group-bearingsilyl polyethers of the invention may take the form wherein theparticles to be modified are modified in a preliminary operation andthen dispersed in the polymer, though it is also possible to add theurethane-group-bearing silyl polyethers in the course of the dispersingof the fillers in the polymer in question, by way, for example, of aliquid feed in an extruder, with an effective dispersing sectionthereafter. Surprisingly, the modification of particle surfaces with theurethane-group-bearing silyl polyethers is generally accomplishedwithout caking or aggregation of the particulate materials to bemodified, in spite of the polyfunctional nature of the prepolymers.

Furthermore, particles surface-modified in accordance with the inventionmay be used, for example, as constituents of reactive diluents,emulsions, wetting agents, paints, adhesion promoters, binders,plasticizers, thixotropic agents, fungicides, flame retardants,pigments, fillers, functional additives in plastics, polymeric foams,organic resins or silicone resins, where appropriate with reactiveattachment to the matrices in question, melt flow index improvers ininjection moulding applications, textile or fibre slip additives,lubricants, matting agents, adsorbents or absorbents, self-dispersibleparticles, particulate emulsifiers, defoamers, binders for ceramicmasses, architectural preservatives, encapsulants, sealing systems,antistatic additives, free-flow aids, microbicidal additives,fluorescent markers, effect pigments, matting agents, release agents,low-temperature-resistant cable coatings, conductive coatings, conductortracks, antistatic coatings, electronic and/or electrical components,rubber parts and membranes, sizes in the textile and glass fibreindustries, paper, additives for toners, abrasives or line fillers incosmetics, formulating agents or carrier materials, colorants andpreservatives, coatings, corrosion inhibitors, inks and/or varnishes,tribological and/or haptic coatings for obtaining physical effects onsurfaces, such as superhydrophobicity, temperature-dependentwettability, beading effects, influencing the dirt pick-up behaviour andthe soil release behaviour on solid surfaces on constructions, textilesof fibres, and also the adhesion of condensates and ice to surfaces andparticles coated in accordance with the invention, and as slip additivesor lubricants, in sealing systems, for obtaining haptic effects, suchas, for example, a silky hand (soft-touch surfaces) or a particularsurface roughness or grip, as matting agents, as points of attachmentfor other materials, such as other coating materials, for example, asadsorbents or absorbents in, for example, paper materials or filtermaterials or fabrics, as self-dispersible particles for producingdispersions, as particulate emulsifiers (for what are called “Pickeringemulsions”; see also “Emulsions”, Spencer Umfreville Pickering, Journalof the Chemical Society, Transactions (1907), 91, 2001-2021), asreactive and/or crosslinkable particles, where appropriate in dispersionin liquid media, as active components in defoamers, in architecturalpreservatives, for example as active components for integralhydrophobisization of materials, as a structured hydrophobic componentfor surface hydrophobisization or as a carrier for active liquidcomponents, as (optionally reactive) encapsulants, such as, for example,for core-shell particles or for the microencapsulation of liquidsystems, for the modification of membrane materials, as for example forobtaining a defined, adjustable porosity, selectivity or permeability,as antistatic additives, for example after hydrophilic or hygroscopicparticle surface modification, as free-flow aids, as additives forobtaining or enhancing scratch resistance on the part of the surfaces ormaterials furnished with the particles, or as particulate additives withother functions, for example as microbicidal additives, as fluorescentlabels or as effect pigments, as release agents, as constituents forlow-temperature-resistant cable coatings, as manufacturing components ofrubber parts and membranes, as a size or ingredients for sizes in thetextile and glass fibre industries, for paper, as additives for toners,as abrasives or line fillers in cosmetics, as carrier materials orformulating ingredients which release auxiliaries or active substancesover a prolonged period of time, the substances which may be present inthe particles and which are to be released being, for example, cosmeticoils and active ingredients, fragrances, active pharmaceuticalingredients, active antimicrobial ingredients, including, for example,silver and compounds containing silver, and also dyes and preservatives,etc.

The inventive formulations when used as a constituent of a formulationdescribed above serve to improve properties such as providing goodadhesion on different substrates, good processability because ofrelative low viscosity, high reactivity in connection with curing,adjustable mechanical properties because of chemical modifications ase.g. elongation, e-module, shore hardness, etc.

The invention accordingly further provides the materials, fabrics andsubstances mentioned above that are coated and are produced using thecurable materials bearing urethane groups.

The reactive curable materials may be used for surface modification oras a coating, as bulk material and also—by suspension polymerization,for example—for preparing particulate materials. Their crosslinking togive solid thermoset end products and fixing to substrates havingrective groups, more particularly hydroxyl groups, are accomplished in asimple way in the presence of water and, optionally, with addition ofacid or base or other accelerants, it being possible to control the rateof cure by increasing the temperature during the curing procedure.

This permits the modification of a wide variety of surfaces, consisting,for example, of metal oxides, mixed oxides, nitrides, hydroxides,carbides, carbonates, silicates, pigments, carbon blacks, elements oralloys, and also surfaces of organic materials. In addition, of course,the surfaces of organic particles, such as those of silicone resins,organically modified silicones, organic polymers or biopolymers, arealso amenable to surface modification.

Hence the curable materials may serve, for example, as base materialsfor the preparation of adhesives, as reactive crosslinkers, as adhesionpromoters and primers, and also binders for metals, glass and glassfibres/glass fabrics, wood, wood-base materials, natural fibres, for thefinishing and treatment of textile or non-textile sheetlike structuresand fibres made from natural and/or synthetic and also mineral rawmaterials, and also, for example, cork, leather, paper, tissue,silicatic and oxidic materials.

The deliberate incorporation of alkoxysilyl moieties which are anchoredvia hydrolytic processes to masonry, concrete, mortar, etc. proves to beextremely advantageous when systems equipped in this way are employed inthe area of the construction industry, in applications involving thejoining and insulating sealing of, for example, frames for windows anddoors in construction shells.

The invention further provides for the hydrophobisization of buildings,using the curable materials as a constituent of water repellents, andthe surface hydrophobicity which can be ensured and tailored as a resultin accordance with the intended application, and which first preventsthe surface being wet through but second allows water vapour to pass.

Particularly in the case of urethane-group-containing silyl polyethershaving a hydrophobic radical or else a high PO, BO or SO content(propylene oxide, butylene oxide and/or styrene oxide content), highhydrophobisization rates can be achieved. Polyethers containing SO, inparticular, are highly suitable, for example, for modifying carbonmaterials, such as graphite and/or carbon black, for example, in orderthat the latter are, for example, more readily dispersible.

The furnishing or treatment of the sheetlike structures serves on theone hand to protect the surface or fibre, to improve its propertiesand/or alter its properties, or to attain new profiles of properties.

Thus, for example, graphite and also hexagonal boron nitride can beincorporated into a silyl polyether containing urethane groups, in orderto produce what are called low-friction coatings. These low-frictioncoatings have “smoothness” as a haptic effect, in contrast, for example,to coatings filled with AEROSIL® 200, which appear very “grippy”.

The invention further provides the tribological and/or haptic coatingsproduced in this way, comprising graphite or boron nitride.

The invention additionally provides sealants and/or adhesives comprisingthe curable materials of the invention, where even a surface coating isalready itself capable of providing sealing or adhesive bonding. Thesesealants and/or adhesives may comprise, in particular, lubricantadditives and also, for example, MoS₂ or PTFE particles.

Furthermore, the curable materials may also find use in the productionof electrical and/or electronic components such as, for example, OLEDsand solar panels. As additives in this case there may be conductiveparticles or ionic liquids present, hence allowing use in conductivecoatings and conductive adhesives, in conductor tracks, for example, forcontacting and/or for antistatic coating.

The curable materials may be utilized alone or as additives in aqueoussystems for the treatment of the stated sheetlike structures and fibres,and thus allow the use of the sheetlike structures and fibres thustreated in the hygiene, medical, construction, automotive, homefurnishing, textile apparel, sport and agricultural sectors.

The particles or sheetlike structures thus surface-modified thereforehave new properties or optimized properties such as in respect, forexample, of softness, lubricity, water transport/absorption, water/oilrepellency, UV protection, self-cleaning (Lotus effect) for awnings, forexample, flame retardancy, an increase in strength in tandem withexcellent flexibility, antistatic properties and resistance to bacteria,viruses and chemicals.

Also provided by the invention, therefore, is a method for the surfacemodification of particles or sheetlike structures, in which the curablematerials are applied, with mixing and/or in the presence of suitablecrosslinking catalysts, in pure form or from suitable organic and/orinorganic solvents, to the particle surfaces, or from emulsions, wherethey are then able to react with covalent or physical attachment.

As surfaces to be modified it is preferred to use organic and/orinorganic particles or sheetlike structures and/or organically modifiedparticles or sheetlike structures and/or mixtures thereof with oneanother.

The invention further provides for the use of the curable materials incosmetic applications, as additives in varnish or nail-varnishformulations.

With the curable materials it is also possible, furthermore, to bringabout specifically physical effects on solid substrates, such ashydrophobic or hydrophilic surface properties, for example. In thiscontext it is also possible, furthermore, for effects of this kind to besubject to an additional stimulus, such as that of the prevailingtemperature, for example. As is known from the literature, polyethers inwater have what are called cloud points, as a function of temperature,which result from the development with increasing temperature ofincompatibility with the surrounding medium. It has been shown that itis possible, via the attachment of silyl polyethers containing urethanegroups to different surfaces, to make their contact angles with respectto various liquids, water for example, a function of temperature.

The invention further provides the production of flame-retardantthermoplastic polymer compounds or thermoset moulding compoundscomprising the curable materials of the invention and able additionallyto comprise flame-preventing and/or flame retardant substances such as,for example, ATH (aluminium trihydrate=aluminium hydroxide aluminiumtrihydroxide) or MDH (magnesium dihydroxide). Polymer compounds of thiskind are employed, for example, for producing cable insulation materialsbased on polypropylene, polyethylene or ethylvinyl acetate for cablesand cable jackets, or flame-preventing partitions are produced on thebasis of polypropylene, for example, which in public buildings such assports halls, for example, are subject to particularly stringentrequirements.

The flame retardant compositions, compounds or electrical cables thustreated may have an improved mechanical stability, improved dispersingof further additives, good extrusion properties, even in the case of ahigh level of filling with particulate additives (as for example withtalc, calcium carbonate, etc.) and also improved flame prevention, orreduced smoke evolution, under strong heating. Particularly when silylpolyethers are used that contain siloxane groups, the silicon contentmay provide additional stability in the event of fire, since, aftercombustion, an additionally stabilizing and fire-retardant SiO₂component is left. Furthermore, even during combustion, the phenomenonknown as skinning is forced to occur at an earlier point in time, andreduces the further increase in the temperature of the material, henceinhibiting the progress of the fire, a factor which is particularlyrelevant in the case, for example, of cables which lead from one roominto the next room.

Additionally provided by the invention are composites such as, forexample, wood-plastic composites (WPCs) produced using the curablematerials. WPCs are thermoplastically processable composites which arecomposed of different proportions of wood, plastics and additives andare processed by thermoplastic shaping techniques, such as, for example,extrusion, injection or compression moulding techniques. As comparedwith polypropylene-maleic anhydride-grafted copolymers, the innovativesilyl polyether composites exhibit enhanced attachment to the wood orfibre substructure of these composites. The curable materials bind tothe fibres based on wood, coconut or other naturally available fibreproducts and at the same time render this surface water repellent,thereby guaranteeing a reduced drying time of the wood fibre pellets(energy saving).

The invention further provides powder coating curing agents.

The invention further provides liquid pastes in which the curablematerials are used alone instead, for example, of a customary polyetherpolyol (PPG 1000), which generally necessitates the additional use of adispersant, since the urethanized silyl polyether combines theproperties of both materials. Pastes of this kind which may comprisepigments as colorants or may further comprise dyes and other additivesare used for the colouring of polyol-based systems such as, for example,PU foams, thermoplastic urethanes or the like.

The curable materials of the invention can be employed, furthermore, asbinders for binding ceramic particles for producing ceramic products,especially refractory ceramic products, from ceramic powder. Theinvention further provides for the use of the binder, and a process forproducing aforementioned ceramic products, and also ceramic products assuch, with refractory ceramic products being particularly preferred inaccordance with the invention.

Refractory ceramic products are used for protection against hightemperatures in numerous industrial plants.

Preference is given to using binders of low to medium viscosity, <10 000mPas, which initially allow complete, uniform envelopment of all ceramicparticles in the preparation phase, as a basis for subsequent attainmentof high crosslinking densities and hence mechanical strengths even ingreen body production, and at temperatures which are already higher inbrown body production or even white body production.

Entirely surprisingly, it has been observed that, when the reactivecurable material of the invention is used as a ceramic binder in thetemperature range between, for example, 100° C. and 1000° C., preferably200° C. and 800° C., there is no decrease or at most only a slightdecrease in the material strength (in comparison with the green bodytreated at lower temperatures), i.e. cold compressive strength [MPa].

For the purposes of this invention, ceramic products include dried,heat-treated and/or fired ceramic products. The term “ceramic product”also encompasses green bodies. In particular, the term “ceramic product”encompasses heat-resistant and/or refractory ceramic products, and alsoshaped bodies and materials which constitute what is called a composite,i.e., are made up of a ceramic material and at least one other materialand/or other phase.

The reactive ceramic binder of the invention, comprising the curablematerial, may be added to the ceramic powder, based on the total weightof the ceramic powder, with a weight fraction of 0.01% to 70% by weight,preferably of 0.1% to 50% by weight and more preferably of 0.5% to 30%by weight, and with particular preference 0.5% to 5% by weight.

Preferred in accordance with the invention are amounts of these curablematerials in the range from 0.05 to <10% by weight, more particularly0.1% to 5% by weight, based in each case on the amount of ceramicpowder. If the amount of the curable material added is below 0.01% byweight, it is very difficult to obtain a fired product of high strength.

In accordance with the invention, the reactive curable material can beused for producing ceramic products, especially shaped and unshaped,fired and unfired refractory ceramic products, from ceramic powder(s).

The present invention therefore further provides ceramic curablematerials containing inventive ceramic binder and ceramic powder(s). Theceramic materials may be used directly or first processed to powders orgranules. The invention also provides for the use of the urethanizedcurable materials of the invention as reactive diluents, emulsions,wetting agents, varnishes, adhesion promoters, plasticizers, thixotropicagents, fungicides, flame retardants, pigments, fillers, polymericfoams, organic resins or silicone resins, melt flow index improvers, inarchitectural preservation, for modifying textiles or fibres, as slipadditives, lubricants, matting agents, adsorbents or absorbents,self-dispersible particles, particulate emulsifiers, defoamers,architectural preservatives, encapsulants, in sealing systems, asantistatic additives, free-flow aids, microbicidal additives,fluorescent markers, effect pigments, release agents,low-temperature-resistant cable coatings, conductive coatings, conductortracks, antistatic coatings, electronic and/or electrical components,rubber parts and membranes, sizes in the textile and glass fibreindustries, paper additives, additives for toners, abrasives or linefillers in cosmetics, formulating agents or carrier materials, dyes andpreservatives, coatings, corrosion inhibitors, paints, tribologicaland/or haptic coatings

Suitable ceramic particles may include all typical, oxidic, non-oxidic,acidic or basic ceramic raw materials and also mixtures thereof.Particular preference is given to ceramic products based on Al₂O₃.Mixtures of these raw materials may also be present.

Ceramic powders which can be used with particular suitability,especially mixtures of ceramic powders, and also their raw materials,include the following:

oxides, such as BeO, MgO, Al₂O₃, SiO₂, CaO, TiO₂, Cr₂O₃, MnO, Fe₂O₃,ZnO, ZrO₂, SrO, Y₂O₃, BaO, CeO₂, UO₂; and/or carbides, such B₄C, Be₂C,Be₄C, Al₄C₃, SiC, TiC, Cr₃C₂, Mn₃C, Fe₃C, SrC₂, YC₂, ZrC, NbC, Mo₂C,BaC₂, CeC₂, HfC, TaC, WC, UC, carbon in the form, for example, ofgraphite, carbon black or graphitisized carbon material; and/ornitrides, such as Be₃N₂, BN, Mg₃N₂, AlN, Si₃N₄, Ca₃N₂, TiN, VN, CrN,Mn₃N₂, Sr₃N₂, ZrN, NbN, Mo₃N₂, HfN, TaN, WN₂, UN; and/or borides, suchas AlB₄, CaB₆, TiB₂, VB₂, CrB₂, MnB, FeB, CoB, NiB, SrB₆, YB₆, ZrB₂,NbB₂, MoB₂, BaB₆, LaB₆, CoB₆, HfB₂, TaB₂, WB, TUB₄; and/or silicides,such as CaSi, Ti₅Si₃, V₅Si₃, CrSi₂, FeSi, CoSi, ZrSi₂, NbSi₂, MoSi₂,TaSi₂, WSi₂; and/or mixtures of the aforementioned ceramic substances.

Further ceramic particles which may be used include oxidic andnon-oxidic compounds, mixed phases, etc., for example, mullite(Al₆Si₂O₁₃), mixed crystals comprising the system Al₂O₃—Cr₂O₃, MgSiO₄,CaSiO₄, ZrSiO₄, MgAl₂O₄, CaZrO₃, SIALON, ALON, and/or B₄C-TiB₂.

It is additionally possible to use ceramic particles having anon-stochiometric composition, such as TiOx silicates, glasses andceramic materials having a metal phase, in accordance with theinvention.

Ceramic particles which can be used in accordance with the invention mayalso comprise calcined aluminas, reactive aluminas, very finely milled,refractory raw materials, such as microsilica, refractory clay and/orbinder clay.

Urethanized prepolymers with a high styrene oxide content as well mayexhibit particularly advantageous properties in the context ofprocessing to form moulding compounds. In particular it is possible todisperse carbon materials, such as carbon blacks or graphites, forexample, effectively in the silyl polyethers 1 of high styrene oxidecontent, leading to advantageous results/properties with regard to themoulding compounds.

The ceramic masses may further comprise catalysts, customary adjuvants,binders and/or additives. The ceramic masses may in particular alsoinclude small amounts of mould release agents, stabilizers and/orpigments.

Furthermore, the use of ceramic masses comprising ceramic binders incombination with hydraulic binders, such as high-alumina cement,portland cement, optionally with water in variable amounts, may likewisebe advantageous.

Based on the total weight of the ceramic powder, the reactive ceramicbinder of the invention may be present in the moulding compound orceramic mass with a weight fraction of 0.01% to 70% by weight,preferably of 0.1% to 50% by weight and more preferably of 0.5% to 30%by weight.

The reaction responsible for binding, namely the reaction betweenceramic powder and the alkoxysilyl-group-bearing, urethane-group-bearingprepolymer of the reactive ceramic binder of the invention, may possiblytake place even at room temperature. As the temperature increases,bonding becomes stronger. Even after a thermal treatment in theintermediate temperature range from 400° C. to 1000° C., or in somecases even from 200° C. to 600° C., the ceramic products are able toattain high strengths, thereby removing the need for high-temperaturefiring at >1000° C.

Surprisingly it has now been found that, when using the ceramic bindersof the invention, comprising urethane-group-containing alkoxysilylprepolymers it is possible

-   -   in a relatively shorter time at the same firing temperatures;        and/or    -   at relatively low firing temperatures in comparable times        to achieve firing of fracture-free ceramic products having        excellent physical and mechanical properties.

The degree of curing is dependent on the shape of the ceramic product.In any case, the shaped ceramic body is cured until it has the strengthnecessary to avoid a change in shape during the firing process.

Additional subject matter of the invention is described by the claims,whose disclosure content in full is part of this description.

The processes and uses of the curable materials, according to theinvention, are described by way of example below, but the inventioncannot be regarded as being confined to these exemplary embodiments.

Where ranges, general formulae or classes of compound are specifiedbelow, they are intended to encompass not only the corresponding rangesor groups of compounds that are explicitly mentioned, but also allsub-ranges and sub-groups of compounds which may be obtained by takingout individual values (ranges) or compounds.

The invention is further described by the following non-limitingexamples which further illustrate the invention, and are not intended,nor should they be interpreted to, limit the scope of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a larger depiction of the silyl polyether 1 of the formula(2).

WORKING EXAMPLES

The examples below were carried out using the following curablematerials, comprising silyl polyethers 1 containing trialkoxysilylgroups, prepared in accordance with specification DE 10 2008 000360.3,not yet laid open, in accordance with the process principle of theDMC-catalyzed alkoxylation of 3-glycidyloxypropyltriethoxysilane(Dynasylan® GLYEO) from Evonik Degussa GmbH. PO denotes propylene oxide.

GPC measurements for determining the polydispersity and average molarmasses were carried out under the following conditions: columncombination SDV 1000/10 000 Å (length 65 cm), temperature 30° C., THF asmobile phase, flow rate 1 ml/min, sample concentration 10 g/l, RIdetector, evaluation against polypropylene glycol standard.

The viscosities were measured in a method based on DIN 53019, using aBrookfield rotational viscometer (model LVT) at 25° C.

The NCO content in percent was determined by back-titration with 0.1molar hydrochloric acid following reaction with butylamine in accordancewith DIN EN ISO 11909.

Trialkoxysilyl Polyether SP-1:

Virtually colourless, high-viscosity silyl polyether with four-foldtrialkoxysilane functionality

Chemical Construction According to Monomer Addition:

Polypropylene glycol monobutyl ether (400 g/mol)+2 mol PO+(21 mol PO/4mol GLYEO random)+2 mol PO

Average molar mass M_(w) 2760 g/mol, polydispersity M_(w)/M_(n) 1.38,viscosity (25° C.) 365 mPa*s.

Trialkoxysilyl Polyether SP-2:

Virtually colourless, high-viscosity silyl polyether with four-foldtrialkoxysilane functionality

Chemical Construction According to Monomer Addition:

Polypropylene glycol (2000 g/mol)+17 mol PO+(103 mol PO/4 mol GLYEOrandom)

Average molar mass M_(w) 10 900 g/mol, polydispersity M_(w)/M_(n) 2.16,viscosity (25° C.) 5050 mPa*s.

Curable Material Comprising the Urethanized Silyl Polyether USP-1:

Preparation, of an NCO- and Urethane-Group-Containing Silyl Polyether

150.2 g (49 mmol, corresponding to 49 mmol of OH functions) of silylpolyether SP-1 were charged to a 250 ml three-neck flask with refluxcondenser, thermometer and KPG stirrer. Then 10.8 g of isophoronediisocyanate IPDI (49 mmol, corresponding to 98 mmol of NCO functions)were metered in slowly at room temperature, and the mixture was admixedwith 0.08 g of dibutyltin dilaurate. The reaction mixture was heated to60° C. and stirred at that temperature for an hour. This gave a clearproduct having a viscosity of 760 MPa*s and an NCO value ofw(NCO)=1.26%.

The initial mass of isophorone diisocyanate was selected to give anexcess of NCO groups over the OH groups of the silyl polyether SP-1,thus forming products which in addition to the alkoxysilyl groups alsostill carry free NCO groups.

Curable Material Comprising the Urethanized Silyl Polyether USP-2:

Preparation of a Urethane-Group-Containing Silyl Polyether

100 g of silyl polyether SP-1 (32 mmol, corresponding to 32 mmol of OHfunctions) were charged to a 250 ml three-neck flask with refluxcondenser, thermometer and KPG stirrer. Then 3.6 g of isophoronediisocyanate (16 mmol, corresponding to 32 mmol of NCO functions) weremetered in slowly at room temperature and the mixture was admixed with0.05 g of dibutyltin dilaurate. The reaction mixture was heated to 60°C. and stirred at that temperature for two hours. This gave a clearproduct having a viscosity of 880 mPa*s and an NCO value of w(NCO)=0%.

The initial mass of isophorone diisocyanate was selected such that theOH groups of the silyl polyether were equimolar with the NCO functions,and so polyethers are linked with one another, and relatively highmolecular mass polyethers are formed.

Curable Material Comprising the Urethanized Silyl Polyether USP-3:

Preparation of a Urethane-Group-Containing Silyl Polyether Having aTriethoxysilyl End Group

100 g of silyl polyether SP-1 (32 mmol, corresponding to 32 mmol of OHfunctions) were charged to a 250 ml three-neck flask with refluxcondenser, thermometer and KPG stirrer. Then 8.0 g of3-isocyanatopropyltriethoxysilane (32 mmol, corresponding to 32 mmol ofNCO functions) were metered in slowly at room temperature. The mixturewas heated to 80° C. and admixed with 0.05 g of dibutyltin dilaurate.The reaction mixture was stirred at this temperature for an hour. Thisgave a product which was clear at room temperature and had a viscosityof 800 mPa*s and an NCO value of w(NCO)=0%.

The initial mass of isocyanatopropyltriethoxysilane was selected suchthat the OH groups of the silyl polyether were equimolar with the NCOfunctions, and so the OH groups are consumed as completely as possibleand the polyethers are modified with further triethoxysilyl groups.

Curable Material Comprising the Urethanized Silyl Polyether USP-4:

Preparation of a Urethane-Group-Containing Silyl Polyether withDesmodur® N 3300

100 g of silyl polyether SP-1 (32 mmol, corresponding to 32 mmol of OHfunctions) were charged to a 250 ml three-neck flask with refluxcondenser, thermometer and KPG stirrer. Then 6.25 g of Desmodur® N 3300(w(NCO)=21.8%, corresponding to 32 mmol of NCO functions) from Bayer(aliphatic polyisocyanate, HDI trimer) were metered in slowly at roomtemperature. The mixture was heated to 80° C. and admixed with 0.05 g ofdibutyltin dilaurate. An exothermic reaction commenced, in the course ofwhich the reaction mixture underwent heating to 105° C. The reactionmixture was subsequently stirred at 80° C. for an hour. This gave aproduct which was clear at room temperature and had a viscosity of 1665mPa*s and an NCO value of w(NCO)=0%.

The initial mass of Desmodur® N 3300 was selected such that the OHgroups of the silyl polyether were equimolar with the NCO functions, sothat the OH groups are consumed as completely as possible, andpolyethers are linked with one another, thus forming a branched silylpolyether.

Curable Material Comprising the Urethanized Silyl Polyether USP-5:

Preparation of a Urethane-Group-Containing Silyl Polyether with IPDI

100 g of silyl polyether SP-2 (10 mmol, corresponding to 20 mmol of OHfunctions) were charged to a 250 ml three-neck flask with refluxcondenser, thermometer and KPG stirrer. Then 1.48 g of Vestanat® IPDI(6.7 mmol, corresponding to 13.4 mmol of NCO functions) from EvonikDegussa GmbH (aliphatic isocyanate) were metered in slowly at roomtemperature. The mixture was heated to 80° C. and admixed with 0.05 g ofdibutyltin dilaurate. The reaction mixture was subsequently stirred at80° C. for an hour. This gave a product which was clear at roomtemperature and had a viscosity of 21 750 mPa*s and an NCO value ofw(NCO)=0%.

The initial mass of Vestanat® IPDI was selected such that the OH groupsof the silyl polyether were in excess over the NCO functions, with theresult that a plurality of polyethers are linked with one another, and,accordingly, a high molecular mass block polyether is constructed.

Curable Material Comprising the Urethanized Silyl Polyether USP-6:

Preparation of a Urethane- and Isocyanate-Group-Containing SilylPolyether with IPDI

150 g of silyl polyether SP-2 (15 mmol, corresponding to 30 mmol of OHfunctions) were charged to a 250 ml three-neck flask with refluxcondenser, thermometer and KPG stirrer. Then 6.67 g of Vestanat® IPDI(30 mmol, corresponding to 60 mmol of NCO functions) from Evonik DegussaGmbH (aliphatic isocyanate) were metered in slowly at room temperature.The mixture was heated to 60° C. and admixed with 0.08 g of dibutyltindilaurate. The reaction mixture was subsequently stirred at 60° C. foran hour. This gave a product which was clear at room temperature and hada viscosity of 16 000 mPa*s and an NCO value of w(NCO)=0.68%.

The initial mass of Vestanat® IPDI was selected so that the OH groups ofthe silyl polyether were in deficit to the NCO functions, with theresult that some of the NCO functions remain in excess, and,accordingly, polymers are formed which carry both NCO groups andalkoxysilyl groups.

Production of Coatings:

20 g of the urethanized silyl polyether, 0.4 g of water and 0.4 g ofdibutyltin diacetylacetonate were weighed out into a beaker and mixedthoroughly using a dissolver at 1000 rpm for 20 seconds. 10 g of thiscurable mixture was poured at room temperature into an aluminium tray.As curing took place, hardening was tested at short intervals using thetip of a pipette. When there is no longer any sticking of the sample, askin has formed. The following skin-forming times were measured, as ameasure of the rate of cure:

Urethanized silyl polyether: Skin-forming time: USP-1 2.5 h USP-2 2.5 hUSP-3 1.5 h USP-4 20 min USP-5 2 h USP-6 2 h

The curing rate of urethanized silyl polyethers carrying NCO groups canbe accelerated by adding amines. In a variant of the aforementionedcuring experiment with USP-1, 17 g of ethylenediamine were addedadditionally to the curable mixture:

Urethanized silyl polyether: Skin-forming time: USP-1 withethylenediamine 30 min

After curing had taken place, the coatings obtained in the aluminiumtray were approximately 2 mm thick.

Preparation of an Aqueous Emulsion:

12.0 g of TEGO® Alkanol S100P (stearyl alcohol, polyoxyethylene (100)ether, Evonik Goldschmidt GmbH), 3.0 g of TEGO® Alkanol TD6(isotridecanol, polyoxyethylene (6) ether, Evonik Goldschmidt GmbH) and15.0 g of water were heated to 60° C. in a glass vessel and stirredusing a Mizer disc at 1000 rpm until a homogeneous, viscous paste wasproduced. With the aid of a dropping funnel, 100.0 grammes of theurethanized silyl polyether USP-1 were incorporated dropwise into thepaste, with stirring, over the course of 30 minutes. When complete, thepaste was stirred at 1000 rpm for 10 minutes. Thereafter the paste wasdiluted with the remaining 200 g of water. This gave an emulsion.

The droplet size distribution was measured by means of dynamic lightscattering (Malvern HPPS with 633 nm HeNe laser). The evaluation of thecorrelation function using the CONTIN algorithm indicated a monomodaldroplet size distribution, with an average radius of 115 nm.

Method for Use as Ceramic Binder in the Production of RefractoryMaterials:

A high-purity sintered α-alumina, T60 available from ALMATIS GmbH atLudwigshafen, having the following particle distribution:

Coarse particles 1 to 2 mm 50% by weight Medium particles 0.2 to 0.5 mm10% by weight Flour <0.1 mm 40% by weightwas mixed homogeneously with 4 parts by weight of each of theurethanized silyl polyethers. The mixtures were used to producecylindrical test specimens with a diameter of 36 mm, under a pressingpressure of 100 MPa, which was subsequently fired at 200° C. and 1500°C. for 2 h.

After firing had taken place, the cold compressive strength [MPa; DIN EN993-1] of the ceramic test specimens was as follows

Urethanized Silyl Polyether USP-1:

Firing temperature 200° C.: 13.5 MPa

Firing temperature 1500° C.: 96.3 MPa

Urethanized Silyl Polyether USP-4:

Firing temperature 200° C.: 14.7 MPa

Firing temperature 1500° C.: 106.1 MPa

Varnish Coating of a Glass Plate:

Using a pipette, 1.00 ml of dibutyltin diacetylacetonate was added to 50ml of urethanized silyl polyether USP-6. The two components werehomogenized using a Mizer disc at 1000 rpm. A layer of prepolymer with athickness of 150 micrometers was applied using a bar applicator to a dryglass plate which had been cleaned with isopropanol. The urethanizedprepolymer applied cures at room temperature and approximately 60%relative atmospheric humidity to form a clear film.

Having thus described in detail various embodiments of the presentinvention, it is to be understood that the invention defined by theabove paragraphs is not to be limited to particular details set forth inthe above description as many apparent variations thereof are possiblewithout departing from the spirit or scope of the present invention.

The invention claimed is:
 1. A curable material comprising:urethane-group-containing reaction products, which is obtainable byreacting: a) at least one compound containing one or more isocyanategroups with; b) at least one compound bearing one or more alkoxysilylgroups and additionally bearing at least one hydroxyl group; c)optionally in the presence of one or more catalysts; d) optionally inthe presence of further components reactive towards the reactionproducts; and e) optionally in the presence of further compounds whichare not reactive towards the reaction products and reactants; whereincomponent (b) is one or more silyl polyethers 1 of the formula (2):

where: a is an integer from 1 to 3; b is an integer from 0 to 2, and thesum of a and b is 3; c is an integer from 0 to 22; d is an integer from2 to 500; e is an integer from 2 to 10,000; f is an integer from 0 to1,000; g is an integer from 0 to 1,000; h, i, and j independently of oneanother are integers from 0 to 500; n is an integer between 2 and 8; Rindependently at each occurrence represents a radical selected fromlinear or branched, saturated, alkyl radicals having 1 to 20 carbonatoms or haloalkyl groups having 1 to 20 carbon atoms; R¹ is a hydroxylgroup or a saturated linear, branched or cyclic oxyorganic radicalhaving 1 to 1500 carbon atoms, that is optionally further substituted,wherein the chain is optionally interrupted by a heteroatom or a radicalcomprising an oxyaromatic system; R² and R³ are independently of oneanother, H, or a saturated or singly or multiply unsaturated monovalentor polyvalent hydrocarbon radical that is optionally furthersubstituted, wherein R² and R³ are optionally bridged via the fragmentY; R⁵ and R⁶ are independently of one another, H, or a saturated orsingly or multiply unsaturated monovalent hydrocarbon radical that isoptionally further substituted; Y is absent, or else is a methylenebridge having one or two methylene units; if Y is absent, then at leastone of R² or R³ independently of one another is a linear or branchedhydrocarbon radical having 1 to 20 carbon atoms; R⁴ independently ateach occurrence is a linear or branched alkyl radical of 1 to 24 carbonatoms or an aromatic or cycloaliphatic radical, which optionally furthercomprises alkyl groups; R⁷ and R⁸ are independently of one anothereither hydrogen or an alkyl, alkoxy, aryl or aralkyl group; and R⁹, R¹⁰,R¹¹, and R¹² are independently of one another either hydrogen or analkyl, alkenyl, alkoxy, aryl or aralkyl group, wherein R¹⁰ and R¹¹ areoptionally bridged via the fragment Z, wherein Z is absent or is adivalent alkylene radical or alkenylene radical; with the proviso thatthe fragments having the indices d, e, f and/or h are present withstatistical distribution or blockwise sequencing.
 2. The curablematerial according to claim 1; wherein component (a) containingisocyanate groups bears no alkoxysilyl and/or alkylsilyl groups.
 3. Thecurable material according to claim 1; wherein, based on the individualmolecule of the reaction product, there are on average more than onealkoxysilyl group per urethane or reaction product thereof.
 4. Thecurable material according to claim 1, further comprising: compoundshaving at least one isocyanate, hydroxyl, amino, epoxy, or unsaturatedC═C group.
 5. The curable material according to claim 4, wherein thereactive silanes are those of the formula (4):U_(x)SiV_((4-x))  (4); where: U represents identical or different groupswhich are non-hydrolysable in the presence of water and catalyticamounts of Brønsted acid at temperatures of up to 100° C.; V representsidentical or different groups which are hydrolysable in the presence ofwater and catalytic amounts of Brønsted acid at temperatures up to 100°C., or hydroxyl groups; and x is 1, 2, 3, or 4; and/or wherein thesilyl-functional compounds are those of the formula (5):

where: X¹, X², and X³ independently of one another are alkyl or alkoxyradicals having 1-8 C atoms; A represents a carboxyl, carbamate, amide,carbonate, ureido, or sulphonate group containing radical, or denotes anoxygen atom; w is an integer from 1 to 8; and v is an integer from 1 to20; and wherein the polymer radical is selected from a group consistingof alkyd resins, oil-modified alkyd resins, saturated and unsaturatedpolyesters, natural oils, epoxides, polyamides, polycarbonates,polyethylenes, polypropylenes, polybutylenes, polystyrenes,ethylene-propylene copolymers, (meth)acrylates, (meth)acrylamides andsalts thereof, phenolic resins, polyoxymethylene homopolymers andcopolymers, polyurethanes, polysulphones, polysulphide rubbers,nitrocelluloses, vinyl butyrates, vinyl polymers, ethylcelluloses,cellulose acetates and butyrates, rayon, shellac, waxes, ethylenecopolymers, organic rubbers, polysiloxanes, polyethersiloxanes, siliconeresins, polyethers, polyether esters, and polyether carbonates.
 6. Thecurable material according to claim 1, further comprising: one or moreblowing agents.
 7. A method of improving the adhesive properties of acomposition selected from the group consisting of curable compositions,adhesives, sealants, sealing compounds, binders, surface-coatingmaterials, reactive crosslinkers, adhesion promoters, water repellents,wetting agents, primers and surface modifiers, architectural waterrepellents, additives in lacquer formulations, nail varnishformulations, reactive diluents, emulsions, wetting agents, paints,adhesion promoters, binders, plasticisizers, thixotropic agents,fungicides, flame retardants, pigments, fillers, functional additives inplastics, polymeric foams, organic resins or silicone resins,melt-flow-index improvers, slip additives for textiles or fibres,lubricants, matting agents, adsorbants and absorbants, self-dispersibleparticles, particulate emulsifiers, defoamers, binders for ceramiccompositions, architectural preservatives, encapsulants, sealingsystems, antistatic additives, free-flow aids, microbicidal additives,fluorescent markets, effect pigments, matting agents, release agents,low-temperature-resistant cable coatings, conductive coatings, conductortracks, antistatic coatings, electronic and electrical components,rubber parts and membranes, sizes in the textile and glass fibreindustries, paper, additives for toners, abrasives and line fillers incosmetics, formulating agents and carrier materials, dyes andpreservatives, coatings, corrosion inhibitors, inks, varnishes,tribological, and haptic coatings, the method comprising: adding thecurable material of claim 1 to said composition.
 8. A method ofimproving the adhesive properties on or for a macroscopic or microscopicsubstrate comprising a material selected from the group consisting of:metals and metal oxides, glass and glass fibres/glass fabrics, wood,wood-based materials, natural fibres, cork, silicatic materials,concrete, mortar, plaster, masonry, particles, oxidic particles, fumedsilica, precipitated silicas, quartz particles and other inorganic oxideparticles, glass particles, titanium dioxide, aluminium oxide, zirconiumdioxide, cerium dioxide, iron oxides, copper oxides, kaolin,wollastonite, talc, mica, feldspars, hydroxides, aluminium trihydroxide,magnesium dihydroxide, boehmite, hydrotalcite and hydroxydic ironpigments, FeO(OH), carbonates, calcium carbonate and dolomite, iron,copper, zinc, nickel, aluminium, magnesium, metal alloys andcarbon-containing materials, graphite and carbon black, organicparticulate substrates, silicone resins, organically modified silicones,organic polymers and biopolymers, leather, tissue, paper, and mixturesthereof, the method comprising: adding the curable material of claim 1to the macroscopic or microscopic substrate.
 9. A method of improvingthe adhesive properties of solutions of emulsions, or suspensions, orfoams, the method comprising: adding the curable material of claim 1 tothe solutions of emulsions, or suspensions, or foams.
 10. The methodaccording to claim 9; wherein the emulsions and/or suspensions comprisecompounds selected from the group consisting of catalysts, photolatentbases, additives for modifying the rheological properties, hydrophilicfillers, organofunctional and/or partially soluble and/orwater-insoluble silanes and/or siloxanes, auxiliaries, film formers,antimicrobial and preservative substances, dispersants, defoamers anddeaerating agents, dyes, colorants and pigments, anti-freeze agents,fungicides, adhesion promoters and/or reactive diluents, plasticizersand complexing agents, spraying assistants, wetting agents, vitamins,growth substances, hormones and/or fragrances, light stabilizers,free-radical scavengers, UV absorbers, and stabilizers.
 11. A method forgenerating antistatic surfaces and/or as starting material for theproduction of rubber parts on the basis of polypropylene oxide,comprising: adding the emulsions and/or suspensions according to claim10 as base materials for varnishes, inks, release agents, adhesives,cosmetic products, scratch-resistant coatings, architecturalpreservatives, corrosion inhibitors, and/or sealants, for coating paper,particles, textile fibres, or glass fibres, or as coating fillers forpaper.
 12. A method of joining surfaces comprising: providing a curablematerial according to claim 1 and applying the curable material to atleast one of the surfaces to be joined or between the surfaces to bejoined; and adhesively bonding the surfaces to be joined with curing.13. The method according to claim 12; wherein the curable material isapplied in the form of a foam.
 14. A method of sealing or bridging orfilling surfaces, cracks, or gaps, comprising: providing a curablematerial according to claim 1 and applying the curable material betweenthe surfaces, cracks, or gaps to be sealed, bridged, or filled, followedby curing.
 15. The method according to claim 14; wherein the curablematerial is applied in the form of a foam.
 16. A method forsurface-modifying particles or sheet structures, comprising: providingthe curable material according to claim 1, with mixing and/or in thepresence of suitable crosslinking catalysts, as they are or fromsuitable organic or inorganic solvents, to the particle surfaces orsheetlike structures, or from emulsions, and then reacting thereon withcovalent or physical attachment.
 17. The method according to claim 16;wherein the surfaces to be modified that are used are inorganic and/ororganic particles or sheetlike structures and/or organically modifiedparticles or sheetlike structures and/or mixtures thereof with oneanother.